Castep PDF

CASTEP GUIDE
MATERIALS STUDIO 2020

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Contents
Chapter 1: CASTEP 1 Constraints 24
Introduction 1 Non-linear constraints 24
Additional Information 1 Potential pitfalls 25
Chapter 2: Tasks in CASTEP 2 Setting up a molecular dynamics
CASTEP Energy task 3 calculation 25
CASTEP Geometry Optimization task 3 Defining the time step 26
Equation of state calculation 4 Choosing an ensemble 26
Geometry optimization methods 5 Constraints 27
CASTEP Dynamics task 5 Setting up a transition state calculation 27
Selecting the thermodynamic ensemble 5 Setting up a transition state confirmation
calculation 28
Defining the time step 5
Setting up an elastic constants
Constraints during dynamics 6
calculation 29
CASTEP Elastic Constants task 6
Setting up strain patterns 29
CASTEP Transition State Search task 6
Convergence criteria 29
Synchronous transit methods 7
Setting up a DFT+U (LDA+U) calculation 30
CASTEP TS Confirmation task 7
Setting up a core hole calculation 31
CASTEP Properties 8
Setting up a work function calculation 32
Modeling disorder in solids 9
Setting up a reaction kinetics calculation 33
Mixture atoms 9
Setting up a calculation on an isolated
Technical limitations 9 molecule 34
Setting up CASTEP calculations 10 Requesting electronic, structural, and
Setting electronic options 11 vibrational properties 35
Setting the quality of a calculation 11 Requesting band structure 35
Setting system parameters 14 Requesting core level spectroscopy 36
Setting the exchange-correlation Requesting density of states 37
functional 15 Requesting electron density difference
Setting up pseudopotentials 17 analysis 38
Setting up the basis set 20 Requesting electron localization
Setting up k-points 22 function 39
Setting up SCF parameters 22 Requesting electronic excitations (TD-

DFT) 39
Setting up a geometry optimization 24
Requesting Fermi surface data 40
Convergence criteria 24
Requesting NMR properties 41
Geometry optimization algorithm 24
Requesting optical properties (DFT) 44
Materials Studio 2020 • CASTEP Guide | Page i

Contents
Requesting orbital analysis 44 Displaying optical properties 71

Requesting vibrational properties 45 Dielectric function calculation 71
Requesting polarizability, IR, and Display optical constants 72
Raman spectra 50 Displaying phonon dispersion and
Requesting population analysis 51 density of states 73
Requesting stress analysis 52 Displaying population analysis results 74
Manipulating files 52 Displaying computed charges, spins,
Input files 52 and bond orders 74
Output files 53 Calculating reaction kinetics 75
Restarting a CASTEP calculation 53 Displaying the averaged potential chart
for work function calculations 76
Analyzing CASTEP results 54
Updating structure 76
Displaying trajectory and chart data 54
Creating a trajectory file 77
Creating a trajectory and chart 55
Displaying thermodynamic properties 77
Animating the trajectory 55
Chapter 3: CASTEP jobs 79
Chart Viewer point selection 55
Using CASTEP job control 79
Visualizing volumetric data 56
Running CASTEP jobs in parallel 79
Electronic charge 56
Remote CASTEP jobs 79
Electron density difference 57
A sample CASTEP run 80
Electron localization function 58
If a remote CASTEP job fails 82
SCF local potential 58
Running CASTEP in standalone mode 83
Orbitals 59
CASTEP file formats 85
STM profile 60
CASTEP file formats - PARAM 86
Field visualization 60
CASTEP file formats - CELL 86
Displaying band structure charts 61
CASTEP file formats - CASTEP 87
Displaying core level spectra 62
CASTEP file formats - binary checkpoint
Displaying density of states charts 63
files 87
Full density of states 63
CASTEP file formats - BANDS 87
Partial density of states 64
CASTEP file formats - CST_ESP 87
Calculating elastic constants 65
CASTEP file formats - task-specific files 88
Description of the elastic constants file 65
CASTEP file formats - PHONON 88
Visualizing Fermi surfaces 68
CASTEP file formats - TDDFT 88
Visualizing vibrational spectra 69
CASTEP file formats - PDOS_WEIGHTS 89
IR spectra 69
CASTEP file formats - CST_OME 89
Raman spectra 70
CASTEP file formats - ORBITALS 89
Displaying NMR results 70
CASTEP file formats - CHDIFF 89
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Contents
CASTEP file formats - ELF 89 CASTEP

CASTEP file formats - OTFG 89 Theoretical limitations 112
Reaction Kinetics Study Table 90 Technical limitations 113
Chapter 4: Theory in CASTEP 92 Test results 113
CASTEP background theory 92 Bulk modulus of NaCl/KCl solid
Supercell approach 92 solution 113
Fast Fourier transforms (FFT) in CASTEP 94 The structure of bicchulite 114
Exchange-correlation functionals in The structure and stability of Pb
CASTEP 95 (Zr,Ti)O3 perovskites 114
Local exchange-correlation functionals The structure of leucite 115
in CASTEP 95 Geometry optimization 116
Gradient corrected exchange- BFGS geometry optimization 116
correlation functionals in CASTEP 95 Constraints 116
Meta-GGA functional 96 Non-linear constraints 117
Nonlocal exchange-correlation Estimated compressibility 117
functionals in CASTEP 96
TPSD geometry optimization 118
Spin Orbit Coupling 97
Damped molecular dynamics 118
DFT+U (LDA+U) 98
Dynamics 118
Symmetry in CASTEP 98
Wavefunctions and density
Pseudopotentials 98 extrapolation 119
Norm-conserving pseudopotentials 100 Ensembles 120
Ultrasoft pseudopotentials 102 NVE ensemble 120
Nonlinear core correction 105 Nosé NVT dynamics 121
Real-space representations of Langevin NVT dynamics 121
pseudopotentials 106
NPT ensemble 121
Plane wave basis set 107
NPH ensemble 123
Finite basis set correction 108
Constraints 123
Self-consistent electronic minimization 108
Example 123
Preconditioning 109
Core level spectroscopy 124
Density mixing schemes 109
Emission spectroscopy 124
Treatment of metallic systems 110
Absorption spectroscopy 125
Disorder in solids 111
Core hole effects 125
Atom occupancy 111
Energy broadening 125
Mixture atoms 111
Spin-orbit splitting 126
Disorder and first principles calculations 111
Phonon density of states 126
Limitations of VCA implementation in 112
Electron localization function 127
Materials Studio 2020 • CASTEP Guide | Page iii

Contents
Formulation of electron localization Quasiparticles and the DFT bandgap 140

function 127 Excitonic effects 140
How to interpret ELF 128 Other limitations 140
Mulliken population analysis 128 Sensitivity of optical properties to
Introduction 128 calculation parameters 140
Formalism 128 Number of conduction bands 140
The LCAO Basis Set 130 Energy cutoff 141
Implementation details 130 Number of k-points in the SCF
Interpreting the results 131 calculation 142
Hirshfeld charge analysis 132 Number of k-points for Brillouin zone
integration 143
Calculating NMR shielding tensors using
pseudopotentials 132 TD-DFT optics 144
All-electron magnetic response with Phonons 144
pseudopotentials 132 Practical schemes for phonon
Calculation of perturbed wavefunctions 133 calculations 146
NMR properties of molecules and Interpolation schemes 147
crystals 133 Finite displacement: supercell method 147
NMR shielding tensor 133 Linear response: Fourier interpolation 147
Sensitivity of NMR to calculation Symmetry analysis of vibrations 147
parameters 134 Infrared spectra 147
NMR J-couplings 135 Linear response 148
EPR G-tensor 136 Raman spectra 149
Optical properties 136 Thermodynamic calculations 151
Definition of optical constants 136 Chapter 5: Dialogs in CASTEP 153
Connection to experimental CASTEP Calculation dialog 153
observables 138
Setup tab 153
Connection to electronic structure 138
CASTEP Geometry Optimization dialog 157
DFT optics 138
CASTEP Dynamics dialog 162
Evaluation of the dielectric constant 138
CASTEP Elastic Constants dialog 165
Details of the calculation 139
CASTEP Transition State Search dialog 167
Evaluation of matrix elements 139
CASTEP TS Confirmation dialog 168
Drude correction 139
Electronic tab 169
Polarization 139
CASTEP Electronic Options dialog 171
Scissors operator 139
Properties tab 181
Limitations of the method 140
Band structure selection 182
Local field effects 140
Core level spectroscopy selection 184
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Contents
Density of states selection 185 CASTEP Phonon DOS Analysis Options

Electron density difference selection 188 dialog 217
Electron localization function selection 188 Population analysis selection 218
Electronic excitations (TD-DFT) Potentials selection 218
selection 189 Reaction kinetics selection 219
NMR selection 189 Raman spectrum selection 220
Optical properties selection 191 STM profile selection 221
Orbitals selection 194 Structure selection 221
Phonons selection 194 Thermodynamic properties selection 222
Polarizability, IR and Raman spectra Results file selector 223
selection 198 Chapter 6: CASTEP keywords 224
Population analysis selection 199 Appendix I: CASTEP References 225
Stress selection 200
Job Control tab 200
CASTEP Job Control Options dialog 201
CASTEP Job Files dialog 202
CASTEP Analysis dialog 203
Band structure selection 203
Core level spectroscopy selection 205
CASTEP EELS Analysis Options dialog 206
Density of states selection 206
CASTEP DOS Analysis Options dialog 208
Elastic constants selection 209
Electron density selection 209
Electron density difference selection 210
Electron localization function selection 210
Energy evolution selection 211
Fermi surface selection 211
IR spectrum selection 212
NMR selection 212
Optical properties selection 213
Optics Analysis Options dialog 214
Orbitals selection 215
Phonon dispersion selection 215
Phonon density of states selection 216
Materials Studio 2020 • CASTEP Guide | Page v

Chapter 1: CASTEP
Introduction
CASTEP is a state-of-the-art quantum mechanics-based program designed specifically for solid-state
materials science. CASTEP employs the density functional theory plane-wave pseudopotential method,
which allows you to perform first-principles quantum mechanics calculations that explore the properties
of crystals and surfaces in materials such as semiconductors, ceramics, metals, minerals, and zeolites.
Typical applications involve studies of surface chemistry, structural properties, band structure, density
of states, and optical properties. CASTEP can also be used to study the spatial distribution of the charge
density and wavefunctions of a system.
In addition, you can use CASTEP to calculate the full tensor of second-order elastic constants and related
mechanical properties of a crystal (Poisson coefficient, Lamé constants, bulk modulus). The transition-
state searching tools in CASTEP enable you to study chemical reactions in either the gas phase or on the
surface of a material using linear synchronous transit/quadratic synchronous transit technology. These
tools can also be used to investigate bulk and surface diffusion processes.
CASTEP can be used effectively to study properties of both point defects (vacancies, interstitials, and
substitutional impurities) and extended defects (for example grain boundaries and dislocations) in
semiconductors and other materials.
Furthermore, the vibrational properties of solids (phonon dispersion, total and projected density of
phonon states, thermodynamic properties) can be calculated with CASTEP using either the linear
response methodology or the finite displacements technique. The results can be used in various ways,
for instance, to investigate the vibrational properties of adsorbates on surfaces, to interpret
experimental neutron spectroscopy data or vibrational spectra, to study phase stability at high
temperatures and pressures, and so on. The linear response method can also be used to calculate the
response of a material to an applied electric field - polarizability for molecules and dielectric permittivity
in solids - and to predict IR spectra.
CASTEP can be used to calculate the properties required to analyze the results of solid-state NMR
experiments, that is, chemical shifts and electric field gradients on atoms of interest. A detailed review of
the CASTEP NMR formalism and numerous examples of practical applications are discussed in
Bonhomme et al. (2012).
The CASTEP STM analysis tool allows you to model scanning tunneling microscopy images at different
bias voltages in order to solve the surface structures based on the experimental STM images.
In all publications arising from your use of CASTEP, please cite:
Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. J.; Refson, K.; Payne, M. C. "First
principles methods using CASTEP", Zeitschrift fuer Kristallographie, 220 (5-6), 567-570 (2005).
Additional Information
For additional information about BIOVIA Materials Studio and other Dassault Systèmes software
applications, visit the Dassault Systèmes Customer Support site:
https://www.3ds.com/support/
Materials Studio 2020 • CASTEP Guide | Page 1

Chapter 2: Tasks in CASTEP
The CASTEP module allows you to perform first-principles quantum mechanical calculations in order to
explore the properties of crystals and surfaces in the solid state. CASTEP can currently perform several
different tasks:
Single-point energy calculation
Geometry optimization
Molecular dynamics
Elastic constants calculation
Transition state search
Transition state confirmation
Properties
Each of these calculations can be set up so that it generates specified chemical and physical properties.
An additional task, known as a properties calculation, allows you to restart a completed job to compute
additional properties that were not calculated as part of the original run.
There are a number of steps involved in running a CASTEP calculation, which can be grouped as follows:
Structure definition: A periodic 3D Atomistic document containing the system of interest must be
specified. There are a number of ways to prepare a structure:
Periodic structures can be built using the tools available in the Materials Visualizer for building
crystals, surfaces, and single-wall nanotubes.
Existing structures can be modified using the Materials Visualizer sketching tools
Structures can be imported from an existing structure file
In the case of a transition-state search, a 3D Atomistic Trajectory document containing a reaction
sequence is required as the input document. You should define the structures of the reactants and
the products in two separate 3D Atomistic documents using the methods listed above and then use
the Reaction Preview tool to generate the trajectory.
Note: CASTEP can only be used to perform calculations on 3D periodic structures. If you wish to
study a molecular system using CASTEP, you will need to construct a supercell to use as the input
structure.
Note: CASTEP cannot handle structures containing pi-system objects. Such objects should be
removed from the document prior to running a CASTEP calculation.
Note: CASTEP performance can be greatly increased if the symmetry of the structure is taken into
account. CASTEP offers an option of finding and using the symmetry automatically if the input
structure is described as having a P1 symmetry. This option is particularly relevant for calculations
on molecular crystals and crystal surfaces, since these structures are typically created as P1 (or p1)
systems. Automatic conversion to a higher symmetry structure will honor all atomic properties
that are relevant to the current CASTEP settings, such as constraints and electronic configuration.
Page 2 | Materials Studio 2020 • CASTEP Guide

Tip: The time required for a CASTEP calculation increases with the cube of the number of atoms in
the system. Therefore, it is recommended that you use the smallest primitive cell description of
your system whenever possible. Select Build | Symmetry | Primitive Cell from the menu bar to
convert to a primitive cell.
Calculation setup: Once a suitable 3D structure document has been defined, then it is necessary to
select the type of calculation to be performed and set the associated parameters. For example, in the
case of a dynamics calculation, these parameters include the ensemble and its settings, the
temperature, and the number and length of the time steps. Finally, the server on which the
calculation is to be run should be selected and the job initiated.
Analysis of the results: When the calculation is complete, the files related to that job are returned to
the client and, where appropriate, displayed in the Project Explorer. Some further processing of
these files may be required to obtain observables such as optical properties. The tools on the CASTEP
Analysis dialog may be used to visualize the results of the calculation.
To select a CASTEP task
1. Choose Modules | CASTEP | Calculation from the menu bar to display the CASTEP Calculation
dialog.
2. Select the Setup tab.
3. Select the required CASTEP task from the Task dropdown list.
CASTEP Energy task

The CASTEP Energy task allows you to calculate the total energy of the specified 3D periodic system, as
well its physical properties.
In addition to the total energy, the forces on atoms are reported at the end of the calculation. A charge
density file is also created, allowing you to visualize the spatial distribution of the charge density using
the Materials Visualizer. The electronic energies at the Monkhorst-Pack k-points used in the calculation
are also reported, so that you can generate a density of states chart during CASTEP analysis.
The Energy task is useful for studying the electronic properties of systems for which reliable structural
information is available. It can also be used to calculate an equation of state (that is, a pressure-volume
and/or energy-volume dependence) for high-symmetry systems with no internal degrees of freedom, as
long as the Stress property is specified.
Note: In systems with internal degrees of freedom, the equation of state can be obtained using the
Geometry Optimization task.
The default unit of energy in CASTEP is the electron-Volt (eV). The relationship between eV and other
popular energy units are found in Mohr et al., 2008:
1 eV 0.0367493254 Ha 23.0605 kcal/mole 96.4853 kJ/mole
CASTEP Geometry Optimization task

The CASTEP Geometry Optimization task allows you to refine the geometry of a 3D periodic system to
obtain a stable structure or polymorph. This is done by performing an iterative process in which the
coordinates of the atoms and possibly the cell parameters are adjusted so that the total energy of the
structure is minimized.

CASTEP geometry optimization is based on reducing the magnitude of calculated forces and stresses
until they become smaller than defined convergence tolerances. It is also possible to specify an external
stress tensor to model the behavior of the system under tension, compression, shear, and so on. In
these cases the internal stress tensor is iterated until it becomes equal to the applied external stress.
The process of geometry optimization generally results in a model structure that closely resembles the
real structure.
The accuracy of the lattice parameters calculated using CASTEP is illustrated in Figure 1 (Milman et al.,
2000).
Figure 1. Experimental vs. CASTEP calculated lattice parameters
Equation of state calculation

Geometry optimization under applied hydrostatic pressure can be used to determine the bulk modulus
of a material, B, and its pressure derivative, B'=dB/dP. The procedure involves calculating a theoretical
equation of state, EOS, which describes the dependence of the cell volume on the external hydrostatic
pressure. The methodology is very similar to the real experiment: the external pressure is fixed using the
Minimizer tab on the Geometry Optimization dialog and the cell volume at that pressure is found by
carrying out geometry optimization with CASTEP.
The subsequent analysis of the P-V dataset is exactly the same as in experimental studies (see Winkler,
1999 for more details). An analytical expression is chosen to describe the EOS and its parameters are
fitted to the calculated datapoints. The most popular form of EOS is the third order Birch-Murnaghan
equation:
Where:

V0 is the equilibrium volume

A detailed comparative study of various analytical forms of EOS was performed by Cohen et al.(2000).
Note: The values of B and B' obtained from such fitting experiments depend on the pressure range
used in the calculations. Experimental values obtained using a diamond anvil cell are usually in the
range 0-30 GPa, so this is the range recommended for theoretical studies. It is also important to avoid
using negative values of pressure in such studies. In addition the pressure values used to create the
P-V dataset should not be uniform. More accurate sampling of the low-pressure region is required to
obtain an accurate value of the bulk modulus.
Geometry optimization methods

By default, CASTEP uses the BFGS geometry optimization method. This method usually provides the
fastest way of finding the lowest energy structure and this is the only scheme that supports cell
optimization in CASTEP.
The Damped molecular dynamics method is an alternative that can be as effective as BFGS for systems
with a flat potential energy surface, for example molecular crystals or molecules on surfaces.
The TPSD geometry optimization algorithm is a viable alternative for systems where the potential energy
surface deviates significantly from the quadratic form. TPSD offers robust convergence and is
particularly recommended when user-supplied constraints on lattice parameters are applied during cell
optimization (for example, when optimizing a solid-solid interface in a direction perpendicular to the
interface plane).
CASTEP Dynamics task

The CASTEP Dynamics task allows you to simulate how the atoms in a 3D periodic structure will move
under the influence of computed forces.
Before performing a CASTEP dynamics calculation you can select the thermodynamic ensemble and
associated parameters and define the simulation time, temperature, and pressure.
Selecting the thermodynamic ensemble

Integrating Newton's equations of motion allows you to explore the constant-energy surface (NVE
dynamics) of a system. However, most natural phenomena occur under conditions where a system
exchanges heat with the environment. These conditions can be simulated using NVT ensembles (either
the deterministic Nosé ensemble or the stochastic Langevin ensemble).
External pressure can be incorporated into the dynamics calculation by using either the NPH (constant
enthalpy) or the NPT (constant temperature) ensemble.
Defining the time step

An important parameter in the integration algorithm is the time step. To make the best use of the
computer time, a large time step should be used. However, if the time step is too large it may lead to
instability and inaccuracy in the integration process. Typically, this is manifested as a systematic drift in
the constant of motion.
Note: Quantum-mechanical molecular dynamics calculations usually require a smaller time step than
forcefield based dynamics applications. However, this is less of an issue in CASTEP because
wavefunction and density extrapolation are used.

Constraints during dynamics

CASTEP supports constraints during molecular dynamics simulations. However, you can only apply
some of the more basic constraints through the Materials Studio interface:
The center of mass can be fixed.
Individual atom positions can be fixed.
Bonds lengths can be fixed.
CASTEP Elastic Constants task

The CASTEP Elastic Constants task allows you to run a set of CASTEP calculations which provides all of
the information necessary to obtain the full 6 × 6 tensor of elastic constants for a 3D periodic structure
with any symmetry.
CASTEP automatically generates the set of distorted structures that is required by symmetry to produce
the full set of elastic constants, then submits jobs for the ideal structure and for all the distorted
structures.
The actual calculation of elastic constants, based on the values of initial strains and calculated stresses, is
performed at the Analysis stage.
The accuracy of the elastic constants, especially of the shear constants, depends strongly on the quality
of the SCF calculation and in particular, on the quality of the Brillouin zone sampling and the degree of
convergence of wavefunctions. Therefore, you should use the Fine setting for SCF tolerance and for k-
point sampling and a Fine derived FFT grid.
It is not necessary to perform geometry optimization before calculating elastic constants, so you can
generate Cij data for the experimentally observed structure. However, more consistent results are
obtained if you perform full geometry optimization, including cell optimization and then calculate the
elastic constants for the structure which corresponds to the theoretical ground state.
Note: Elastic Debye temperature and averaged sound velocity are not reported if the calculated
elastic constants do not produce physically meaningful sound velocities in some directions (for
example, if certain Cij values or their combinations are negative when they should be positive). This
can happen for low quality calculations or for calculations that were not preceded by a geometry
optimization (including optimization of the lattice parameters).
CASTEP minimizes internal coordinates for each distorted structure while keeping the lattice parameters
fixed. It is possible to use either the BFGS or the damped MD geometry optimization method. To select a
different method you have to select the Geometry Optimization task, change the relevant setting and
then return to the Elastic Constants task.
Note: As part of the Elastic Constants task, CASTEP performs a single point energy calculation for the
undistorted structure. This allows you to analyze electronic and volumetric properties. The energy
and stress from this calculation are not used to evaluate the elastic constants.
CASTEP Transition State Search task

The CASTEP TS Search task allows you to optimize a transition state.
When a 3D periodic molecular or crystal structure is built, it usually needs to be refined to bring it to a
stable geometry. The refinement process is known as optimization. It is an iterative procedure in which
the coordinates of the atoms are adjusted so that the energy of the structure is brought to a stationary
point, that is, one in which the forces on the atoms are zero. A transition state is a stationary point that

is an energy maximum in one direction (the direction of the reaction coordinate) and an energy
minimum in all other directions.
During the course of chemical reaction, the total energy naturally changes. Starting from the reactants,
the energy increases to a maximum and then decreases to the energy of the products. The maximum
energy along the reaction pathway is known as the activation energy. The structure corresponding to
this energy is called the transition state.
The TS Search task is particularly useful for predicting barriers to chemical reactions and determining
reaction pathways. It can be also used to find diffusion barriers for either solid state diffusion or surface
diffusion. The reactants and products can either be optimized separately before running a TS Search or
as part of this task. In the latter case partition functions for reactant, product, and transition state can
also be calculated. This information can be used to calculate the reaction rate coefficient.
Synchronous transit methods

CASTEP transition state searches are performed using synchronous transit methods. These work best
when reasonable structures for the reactants and products exist, but the location of the transition state
is unknown.
Starting from reactants and products, the synchronous transit methods interpolate a reaction pathway
to find a transition state. The Linear Synchronous Transit (LST) method performs a single interpolation
to a maximum energy. The Quadratic Synchronous Transit (QST) method alternates searches for an
energy maximum with constrained minimizations in order to refine the transition state to a high degree.
The options available through CASTEP include:
LST Maximum performs a single LST maximization, bracketing the maximum between the reactants
and product. This is the quickest but least accurate of the options. The TS structure determined by
this method generally requires further refinement.
LST/Optimization performs an LST maximization, followed by an energy minimization in directions
conjugate to the reaction pathway. This yields a structure lower in energy and closer to the true TS
than a simple LST. Minimization steps continue until an energy minimum is reached or the number
of conjugate directions is exhausted.
Halgren-Lipscomb is a kind of limited LST/Optimization, and is designed to reproduce the algorithm
popularized by Halgren and Lipscomb. After determining the LST maximum, this method performs a
conjugate gradient minimization, but only in a single direction.
Complete LST/QST begins by performing an LST/Optimization calculation. The TS approximation
obtained in that way is used to perform a QST maximization. From that point, another conjugate
gradient minimization is performed. The cycle is repeated until a stationary point is located or the
number of allowed QST steps is exhausted.
A complete description of the algorithms used is given in Govind et al. (2003).
CASTEP TS Confirmation task
The TS Confirmation tool verifies that a TS calculated by an LST or QST search connects the reactant and
product as expected. See Setting up a TS confirmation calculation for more details on the mechanics of
this method. Materials Studio automatically determines the reactant, TS and product from the given LST
or QST trajectory document.
Use the controls on the CASTEP TS Confirmation dialog to specify the convergence criteria for each
individual geometry optimization (microiteration), and to specify the number of frames to use in the TS
confirmation trajectory.

The output of a TS confirmation calculation is another trajectory document. This one follows the
Intrinsic Reaction Path (IRP) as discussed in Reaction pathways. Each successive refinement to the
pathway is displayed as a graph in Materials Studio. Use the chart selection tools to choose any point on
the graphs and display the corresponding geometry.
In most cases, no minima will be found on the IRP other than your reactant and product. If so, the TS
confirmation calculation verifies that the TS does connect your presumed reactant and product.
On the other hand, any other minima located by the TS confirmation are the structures that are actually
connected by the TS. These are identified with an asterisk (*). You should perform a geometry
optimization to refine the geometry of these minima. Select the structures as described in the Displaying
trajectory and chart data topic.
You can generate a detailed map of the entire reaction by repeating TS Search and TS Confirmation for
all minima on the IRP.
CASTEP Properties
The CASTEP Properties task allows you to compute electronic, structural, and vibrational properties
after the completion of a single-point energy, geometry optimization, or dynamics run on a 3D periodic
system.
Note: In order to calculate properties using the CASTEP Properties task, the results files from a
suitable simulation must be present in the current project.
You can also use the Properties tab on the CASTEP Calculation dialog to request that such properties be
calculated as part of a CASTEP run. You can view the results using the CASTEP Analysis dialog.
The properties that can be generated by CASTEP are:
Band structure: Electronic eigenvalues along high symmetry directions in the Brillouin zone are
calculated non-self-consistently for both valence and conduction bands, using electronic charge
densities and potentials generated during the simulation.
Core level spectroscopy: Electronic energies on the Monkhorst-Pack mesh of k-points and the
matrix elements for electronic interband transitions are calculated, either with or without core holes.
Density of states: Electronic eigenvalues on a fine Monkhorst-Pack grid are calculated non-self-
consistently for both valence and conduction bands, using electronic charge densities and potentials
generated during the simulation.
Electron density difference: The electron density difference with respect to either a linear
combination of the atomic densities or a linear combination of the densities of sets of atoms
contained in the structure is calculated.
Electron localization function: A simple measure of electron localization in atomic and molecular
systems.
Electronic excitations (TD-DFT): Electronic excitations for molecules in a box calculated using the
time-dependent density functional theory (TD-DFT).
NMR: Chemical shielding tensors and electric field gradients are calculated.
Note: NMR in CASTEP is part of the separately licensed module NMR CASTEP. NMR calculations
can only be performed if you have purchased this module.
Optical properties: Matrix elements for electronic interband transitions are calculated. The CASTEP
Analysis dialog can be used to generate grid and chart documents containing measurable optical
properties.

Orbitals: Information about electronic wavefunctions is provided. This allows you to visualize 3D
distribution of various electronic states (orbitals). This information is required also for visualization of
STM profiles.
Phonons: For phonon dispersion runs, phonon frequencies and eigenvectors along high symmetry
directions in the Brillouin zone are calculated. In the case of phonon density of states calculations,
phonon frequencies and eigenvectors are computed on a Monkhorst-Pack grid. This information is
required during analysis to display total and projected (partial) phonon densities of states. It is also
used to calculate thermodynamic properties including atomic displacement parameters, which allow
assignment of temperature factors during analysis.
Note: Phonon calculations take into account existing fixed atom constraints, regardless of the
overall Task setting. Such fixed atoms are excluded from the calculation of vibrational properties,
which corresponds to the "partial Hessian" approach.
Tip: You must check the Fix fractional position checkbox on the Atom tab of the Edit Constraints
dialog, accessible from the Modify menu.
Polarizability, IR and Raman spectra: The optical (ω = ∞) and dc (ω = 0) dielectric permittivity or the
optical (ω = ∞) and static (ω = 0) molecular polarizability, along with infrared or Raman intensities
(response to an electric field in the infrared range) are calculated. Permittivity is relevant for solid
materials, while polarizability and infrared intensities are relevant to molecules prepared using the
supercell approach.
Population analysis: Mulliken analysis and Hirshfeld charge analysis is performed. Mulliken bond
populations and angular momentum-resolved atomic charges (as well as magnetic moments for
spin-polarized calculations) are calculated. Optionally, the weights required for partial density of
states (PDOS) calculations are generated. Hirshfeld atomic charges are produced.
Stress: The stress tensor is calculated and written to a seedname.castep file. This information is
useful if, for example, you perform a geometry optimization run in which cell parameters are fixed
and you want to check how far the lattice is from equilibrium. For instance, a supercell study of a
point defect should be carried out with the fixed cell that corresponds to the theoretical ground state
of the given system. The value of the stress after geometry optimization gives an indication of the
magnitude of the elastic effects associated with the supercell approximation.
Modeling disorder in solids

Many crystal structures possess static positional disorder. Materials Studio allows you to model
disorder by defining mixture atoms.
Mixture atoms
Atomic sites in a disordered crystal can be described in terms of a hybrid atom, which consists of two or
more element types. The relative concentrations can be set for any number of atoms, where the total
concentration must be 100%. The mixture atoms description is the most often used representation of
solid solutions, metallic alloys, disordered minerals, and so on.
Technical limitations
Current implementation of the molecular dynamics (MD) algorithms in CASTEP is not yet compatible
with the virtual crystal approximation (VCA) formalism, which is used to model disorder in solids. None
of the MD schemes (NVE, NPT, and so on) work for disordered crystals in the current version.
The following properties are unavailable for disordered systems:

Population analysis
Vibrational properties (phonon dispersion, phonon density of states)
Optical properties
In addition, geometry optimization based on damped MD is not available (since MD itself is not
allowed).
Atom occupancy cannot be used with the current CASTEP implementation of the virtual crystal
approximation (VCA). Partial atom occupancy can be considered as a special case of a mixture atom,
where one part of the mixture is an atom of "nothing". This case is not supported for a number of
technical and fundamental reasons.
The limitations listed above fall into three categories:
Properties that are ill-defined or do not make sense at all for mixture atoms (population analysis,
vibrational properties).
Features where the calculations might be possible, but which require more theoretical work (optics,
partial atomic occupancies).
Features that are blocked for purely technical reasons (molecular dynamics).
These limitations are imposed by the user interface; if you attempt a run using a combination of settings
which is not allowed, a message box explaining why the run cannot be carried out will be displayed when
you select Run or Save Files.
Setting up CASTEP calculations

The topics in this section describe how to set up CASTEP calculations of various types, as well as the
ways in which the job control facility can be used.
There are a number of options that are understood by CASTEP which are not currently accessible
through the Materials Studio interface. Such options can be utilized by manually editing the CASTEP
input files. Information about how to do this is also presented in this section.
An important concept that affects a large number of settings exposed in CASTEP is that of a calculation
quality. The Quality setting on the Setup tab of the CASTEP Calculation dialog provides a shortcut for
setting up a balance between the accuracy and speed of calculations. The range of values from Coarse to
Ultra-fine allows you to increase the accuracy gradually by imposing more strict tolerances, improving
accuracy of reciprocal space sampling, and increasing the number of basis functions. Nevertheless there
are cases where there is no need to systematically change the quality settings and a fast qualitative
description is sufficient. The Express quality setting is provided to allow many simple cases to get
reasonable results quickly. Please note that these settings cannot be translated into the Coarse - Ultra-
fine accuracy scale. This setting is especially useful for semiconductors and insulators and can be fairly
accurate for nonmagnetic metals. The study of magnetic metallic systems requires more accurate
calculation settings than those defined by the Express quality setting.

Note: CASTEP does not support all possible permutations of electronic settings for all possible
properties requests. In cases where the input settings are contradictory the Materials Studio client
will display messages explaining the problem. However, sometimes the combinations selected during
the setup of a CASTEP calculation are impossible to satisfy. The main source of such contradictions is
in the type of pseudopotentials used. For example, NMR calculations and core level spectroscopy
calculations require the use of on-the-fly generated (OTFG) pseudopotentials for at least some
elements. On the other hand, nonlocal exchange-correlation functionals (for example B3LYP) or linear
response phonon calculations are limited to norm-conserving pseudopotentials. It is therefore
impossible to use the same settings for requesting, for example, phonon dispersion using linear
response and core level spectra, or to calculate band structures with B3LYP and request NMR
chemical shifts.
Tip: Accurate calculations for 3D periodic systems may require a large number of k-points if the lattice
has a strongly skewed unit cell (for example, some cell angles are very small). In such cases it might be
beneficial for the speed of calculations to convert the structure to reduced (Niggli) cell representation
using the Redefine Lattice dialog.
Setting electronic options

Electronic options must be set for Energy, Geometry Optimization, Dynamics, Elastic Constants, and TS
Search calculations. The settings used for Properties calculations are copied from the input files of the
calculation that is to be restarted and are unaffected by any changes made through the interface.
The basic controls used to define the calculations are available on the Setup and Electronic tabs of the
CASTEP Calculation dialog. The important settings that you might need to modify are:
Quality - determines how accurate and how expensive the calculation will be
System parameters - describe the charge and spin state of the system
Exchange-correlation functional - determines the level of the DFT description
Pseudopotentials - affect both the accuracy and the cost of the calculation
Basis set - specifies the quality of the plane wave basis set
k-points - determine the accuracy of the Brillouin zone sampling
SCF - specifies the scheme that is to be used for electronic minimization
Setting the quality of a calculation
An important concept that affects a large number of settings exposed in CASTEP is that of a calculation
quality. The Quality setting on the Setup tab of the CASTEP Calculation dialog provides a shortcut for
setting up a balance between the accuracy and speed of calculations. To help you select appropriate
values for CASTEP parameters, four predefined parameter sets are available. The predefined sets vary in
quality from Coarse, suitable for quick approximate calculations, to Ultra-fine, for calculations where
high precision is required.
CASTEP formalism lends itself naturally to a systematic convergence study by means of increasing the
size of the basis set, accuracy of Brillouin zone sampling, and so on. Nevertheless there are cases for
which there is no need to systematically change the quality settings and a fast qualitative description is
sufficient. The Express quality setting is provided to allow you to obtain reasonable results quickly in
many simple cases. This setting can be an order of magnitude faster than the Fine setting, while
producing results that are sufficiently accurate for exploratory studies, for investigation of qualitative
trends in a high-throughput context for example. The Express setting is especially useful for
semiconductors and insulators and can be fairly accurate for nonmagnetic metals. The study of

magnetic metallic systems usually requires more accurate calculation settings than those defined by the
Express quality setting.
Note: The Express setting cannot be translated into the Coarse - Ultra-fine accuracy scale.
To help you select appropriate values for CASTEP parameters, four predefined parameter sets are
available. The predefined sets vary in quality from Coarse, suitable for quick approximate calculations, to
Ultra-fine, for calculations where high precision is required.
To select a quality
dialog.
3. Choose a Quality setting from the dropdown list to select one of the four predefined parameter
sets.
When you choose a Quality setting, the parameters are set according to the task and the system.
Quality Express Coarse Medium Fine Ultra-Fine

Energy tolerances per Cell Atom Atom Atom Atom
SCF tolerance (eV/atom) 1.0 × 10-5 2.0 × 10-6 1.0 × 10-6 5.0 × 10-7
SCF tolerance (eV/cell) 0.0001
SCF Convergence window 2 3 3 3 3
k-points separation (metals) (Å-1) 0.07 0.07 0.05 0.04 0.04
k-points separation (insulators) (Å-1) 0.1 0.1 0.08 0.07 0.07
Energy cutoff Fine Coarse Medium Fine 1.1 × Fine
FFT Grid Density Standard Standard Standard Fine Precise
Apply finite basis set correction 1 1 1 1.2 1.5
Augmentation density scaling factor Never Smart Smart Smart Smart
The values of the Energy cutoff that correspond to the Coarse, Medium, and Fine settings are element
specific and are taken from the pseudopotential files stored in the database. These values were
determined from convergence tests for single atoms and diatomic molecules and they roughly
correspond to total energy convergences of 2, 0.3, and 0.1 eV atom-1, respectively. The highest value for
the selected quality setting among the elements present in the 3D structure document is accepted.
The Quality setting also affects the values of the convergence tolerances for tasks such as geometry
optimization, elastic constants calculations, and transition-state searching.
Note: The values of force, stress, and displacement tolerances for the Geometry Optimization and
Elastic Constants tasks are set to 100 for ExpressQuality. This preset value instructs CASTEP to ignore
these tolerances and consider only the energy tolerance as a convergence criterion.

Quality Express Coarse Medium Fine Ultra-fine
Energy tolerance (eV/atom) 5.0e-5 2.0e-5 1.0e-5 5.0e-6
Energy tolerance (eV/cell) 0.001
Max. force tolerance (eV/Å) 100 0.1 0.05 0.03 0.01
Max. stress tolerance (GPa) 100 0.2 0.1 0.05 0.02
Max. displacement tolerance (Å) 100 5.0e-3 2.0e-3 1.0e-3 5.0e-4
BFGS Use line search No Yes Yes Yes Yes
Note: The values of force, stress, and displacement tolerances are set to 100 for ExpressQuality. This
preset value instructs CASTEP to ignore these tolerances and consider only the energy tolerance as a
convergence criterion.
The individual tolerances may need to be adjusted in some cases:
The Max. force tolerance can be reduced for molecular systems (isolated molecules, molecules on
surfaces, molecular crystals, and so on)
The Max. stress tolerance is generally expressed as a fraction of the bulk modulus of the material, so
it should be smaller for soft materials. However, in practice, cell optimization of soft substances (for
example, molecular crystals) is difficult and might not be stable enough to impose very stringent
convergence criteria.
Elastic constants
Energy tolerance (eV/atom) 1.0e-5 4.0e-6 2.0e-6 1.0e-6
Energy tolerance (eV/cell) 0.001
Max. force tolerance (eV/Å) 100 0.02 0.01 0.006 0.002
Max. displacement tolerance (Å) 100 1.0e-3 4.0e-4 2.0e-4 1.0e-4
Note: The values of force, and displacement tolerances are set to 100 for ExpressQuality. This preset
value instructs CASTEP to ignore these tolerances and consider only the energy tolerance as a
convergence criterion.
Note: These tolerances are five times more strict than the ones used for the Geometry Optimization
task.
TS Search
RMS convergence (eV/Å) 0.1 0.5 0.25 0.05 0.01

Setting system parameters

System charge
CASTEP allows you to perform calculations on charged systems. This is useful for studies of, for example,
charged defects in semiconductors (Milman et al., 1993 and Hakala et al., 2000).
Note: Makov-Payne corrections, which improve the convergence of the total energy with respect to
the supercell size in charged periodic systems, are not implemented in this version of CASTEP. This
means that the results obtained for charged systems with small unit cells are less reliable.
To set system charge
dialog.
3. Specify the system charge in the Charge field.
Spin polarization
Magnetic systems can be studied by carrying out spin-polarized DFT calculations with CASTEP. This
setting is recommended for transition metal oxides, certain inorganic surface studies, and metallic
systems containing magnetic elements (Fe, Co, Mn, Ni).
Spin-polarized CASTEP calculations are normally carried out with a variable magnetic moment. This
procedure, however, does not guarantee finding the lowest energy state. DFT solutions can converge to
a variety of local minima, so that the metastable states are found. The most commonly obtained
solutions correspond to high spin and low spin states. The state generated by CASTEP depends on the
initial magnetic configuration, since the solution is likely to converge to the nearest local minimum
rather than to the global minimum.
There are two ways of defining the initial magnetic configuration: either specify the total magnetic
moment per unit cell, which gets uniformly distributed over the space, or provide detailed information
on the absolute values and direction (up or down) of the spins for each atom in the unit cell. The former
method can be used for relatively simple systems where only two solutions are expected (magnetic and
non-magnetic). The latter method, which specifies the spin state of the atoms in the system, is more
general and gives much more flexibility. It is possible to set up ferromagnetic, ferrimagnetic, or
antiferromagnetic calculations to get different starting spin arrangements.
To set up a spin-polarized calculation with a uniformly distributed initial magnetic moment
dialog.
3. Check the Spin polarized checkbox and uncheck the Use formal spin as initial checkbox.
4. Specify an Initial spin value.
5. To optimize the spin value, select the Electronic tab and click the More... button to access the
CASTEP Electronic Options dialog.
6. Select the SCF tab.
7. Uncheck the Fix occupancy checkbox and check the Optimize total spin checkbox.

To set up a spin-polarized calculation with a specified ordering of atomic moments

Note: Initial magnetic moments on atoms are treated correctly by CASTEP only when the density
mixing scheme is used for electronic structure minimization. CASTEP will ignore atomic information
and will use the uniformly distributed magnetic moment for the all bands or EDFT minimizers. The
value of the total moment is determined by the sum of formal spins in the system.
1. Set formal spins for the atoms.
2. After setting the formal spins, find and impose the symmetry of the system.
dialog.
5. Check the Spin polarized and Use formal spin as initial checkboxes.
6. Select the Electronic tab and click the More... button to access the CASTEP Electronic Options
dialog.
7. Select the SCF tab.
8. Select Density mixing as the Electronic minimizer setting.
9. Uncheck the Fix occupancy checkbox and check the Optimize total spin checkbox.
It is important to include a sufficient number of empty bands when optimizing the spin state. The
default number of empty bands is 4, which means that the maximum accessible increase in the spin
value is 8. A calculation that started with the low spin state will be extremely slow if the actual minimum
found by CASTEP corresponds to the high spin state (although this is not the case when a calculation
starts with high spin and converges to low spin).
Note: CASTEP might fail to converge the SCF if the number of empty bands is insufficient to
accommodate the high spin state, especially in a calculation with variable occupation numbers
(metallic systems).
Electric fields
An external electric field can be applied to the system. This causes a force to act on each atom which is
proportional to the charge on that atom. This can be used to calculate the polarizability of a dielectric
material.
To apply an electric field
dialog.
2. Select the Electronic tab and click the More... button to access the CASTEP Electronic Options
dialog.
3. Select the Potentials tab.
4. Specify the strength of the Electric field to apply.
5. Enter the Field direction in lattice vectors (A B C).
Setting the exchange-correlation functional
CASTEP supports one local exchange-correlation functional, LDA, three gradient-corrected exchange-
correlation functionals, GGA, and a set of nonlocal functionals for the self-consistent total energy
calculations.

LDA functional
CA-PZ is the only local (LDA) functional available in CASTEP. It is based on the Ceperley and Alder (1980)
data as parameterized by Perdew and Zunger (1981).
GGA functionals
GGA functionals provide a better overall description of the electronic subsystem than the LDA
functionals. The LDA description tends to overbind atoms, so that the bond lengths and the cell volume
are usually underestimated by a few percent and the bulk modulus is correspondingly overestimated.
GGA corrects this error but may underbind instead, leading to slightly long bond lengths.
PBE (Perdew et al., 1996) is the default exchange-correlation functional. It is recommended, especially,
for studies of molecules interacting with metal surfaces, although it is also fairly reliable for bulk
calculations. The PW91 (Perdew et al., 1992) functional should be used for comparisons with literature
data, as it is the most widely used GGA functional. The results obtained with the PW91 functional should
be very similar to those obtained with PBE. Another nonlocal functional, RPBE (Hammer et al., 1999), is a
revised form of the PBE functional designed to improve the description of metallic surfaces. One of the
latest GGA potentials, WC, is due to Wu and Cohen (2006). The authors claim significant improvements
for lattice constants, crystal structures, and metal surface energies over the most popular Perdew-
Burke-Ernzerhof (PBE) GGA. Another recent functional, PBEsol, has been developed specifically to
improve the description of exchange in solids, resulting in better structures and energetics for densely
packed solids and their surfaces (Perdew et al., 2008).
Meta-GGA functional
In addition to the generalized gradient (GGA) functionals, which depend on the local density and its
gradient, CASTEP can handle functionals that depend on the kinetic energy density. The current
supported functional is RSCAN (Bartok and Yates, 2019), which is an improved regularized version of the
SCAN ("Strongly Constrained and Appropriately Normed") functional developed by Sun et al., 2015.
Meta-GGA functionals are considered to be more accurate than pure GGA, and the cost of such
calculations is significantly lower than for nonlocal functionals.
Note: Currently, there are limitations on the use of meta-GGA in CASTEP. The meta-GGA functional is
not compatible with DFT-D corrections, spin-orbit coupling, J-coupling , linear-response phonons, or
polarizability calculations. The formalism cannot be used with mixture atoms. Only on the fly
generated pseudopotentials can be used.
Nonlocal exchange-correlation functionals

Nonlocal exchange-correlation functionals result from the generalized Kohn-Sham procedure (Seidl et
al., 1996) and are intended to improve on the description of band gaps in insulators and semiconductors
compared with LDA or GGA calculations. This additional accuracy comes at the price of more time
consuming calculations.

Several approximations for nonlocal exchange-correlation functionals are available:

HF
HF-LDA
sX
sX-LDA
PBE0
B3LYP
HSE03
HSE06
The recommended functionals are sX-LDA, PBE0, B3LYP and HSE06; the rest are supported mostly for
testing against other packages that implement Hartree-Fock schemes for solids.
Note: There are limitations on the use of this approach: nonlocal exchange can only be used for
insulators using the all-bands minimizer (not density mixing) with the Energy, Geometry
Optimization, and TS Search tasks (without cell optimization). It is not compatible with stress, NMR,
phonon or polarizability calculations. The formalism cannot be used with mixture atoms or ultrasoft
potentials. Note that stress calculations, and hence cell optimization and the Elastic Constants task,
are supported for screened exchange versions, sX and sX-LDA, and for the HSE family of functionals.
To select the exchange-correlation functional
1. Choose Modules | CASTEP | Calculation from the menu bar.
3. Choose a local (LDA), a gradient corrected (GGA) or nonlocal functional from the first dropdown list
for the Functional.
4. Select the specific functional from the second dropdown list.
Setting up pseudopotentials
Ultrasoft and norm-conserving pseudopotentials
CASTEP uses on-the-fly generated ultrasoft pseudopotentials (USP) by default. These are generally more
accurate and more efficient than norm-conserving pseudopotentials (NCP).
USP implementation allows CASTEP calculations to be run with a lower energy cutoff than their NCP
counterparts producing a clear advantage in terms of the calculation time. However, USP formalism is
more complex and becomes close to intractable for such complex concepts as linear response
implementation for phonons or NMR properties, or for nonlocal exchange-correlation functionals. As a
result, there is a number of tasks and properties that CASTEP can address only with norm-conserving
potentials.
There are two types of pseudopotentials available in Materials Studio: tabulated and generated on-the-
fly.
Pseudopotentials generated on the fly
CASTEP server code allows you to generate pseudopotentials on the fly, that is, you can provide the
parameters which govern the generation rather than a tabulated file from the database. This approach
has a number of advantages; for example, the same exchange-correlation functional is used in the
atomic and solid state calculations; it is possible to generate "softer" or "harder" potentials by changing
the core radius; it is possible to study excited configurations with a core hole, and so on.

The latest set of OTFG settings for ultrasoft pseudopotentials has been developed in order to minimize
the error with respect to fully converged all-electron DFT calculations. The error achieved by this set is
0.4 meV/atom, which puts CASTEP among the most accurate pseudopotential codes available. A full
definition of the test framework and the meaning of the error is given by Lejaeghere et al. (2014), and on
the website of the Delta project: http://molmod.ugent.be/deltacodesdft. The files that correspond to
this set have the _2017R2 suffix . This is the recommended set of OTFG ultrasoft potentials. Files with
the _2017R2ncp suffix are recommended when norm-conserving potentials are required (this set has
a 1.1 meV/atom error in the Delta project tests). In addition, a set of "high throughput" ultrasoft OTFG
settings is available for scripting; this QC5 set generally requires lower cutoff energy and offers faster but
less accurate calculations (1.9 meV/atom error in the Delta project tests).
Note: It is not recommended to use PW91 exchange-correlation functional when requesting on the
fly generation of pseudopotentials; PBE, RPBE, WC, BLYP, or PBESOL are better options when a GGA
functional is required.
This scheme has been validated for all elements of the Periodic Table, the results of the tests are
included in the files themselves. It is possible to create customized versions of the pseudopotential
generation settings, but it is recommended to test the resulting potentials thoroughly for convergence
and transferability by performing calculations for a variety of systems and at different energy cutoffs.
The details of the format of the settings file for on the fly generation are provided.
On the fly generation of pseudopotentials involves solution of the electronic structure of an atom and a
pseudoatom, this step can be done either in a non-relativistic (Schroedinger) framework or using one of
the available scalar relativistic approaches (Koelling-Harmon or ZORA). It is important to use a scalar
relativistic treatment for improved accuracy of calculations for heavy elements.
Note: J-coupling can only be computed using the Schroedinger or ZORA approach.
Note: CASTEP NMR calculations can be performed only by using on the fly generation scheme, since
the available potentials in the database do not contain sufficient information about all-electron
projectors.
Tabulated pseudopotentials
Tabulated USP files in the database have a .usp or .uspcc extension, tabulated norm-conserving files
have a .recpot extension.
Note: Different tabulated ultrasoft potentials should be used for LDA and GGA exchange-correlation
functionals. The naming convention in the database is <element name>_<ID>.usp[cc] for
LDA functionals and <element name>_<ID>PBE.usp[cc] for GGA functionals. By default,
Material Studio tries to find the best fit of the potentials to the exchange-correlation potentials,
although this behavior can be overridden.
The database of NCPs available in Materials Studio is rather old and in some cases might contain
potentials that have not been tested sufficiently. An alternative to using this database is to generate
NCPs using the open source software package Opium, yhe Optimized Pseudopotential Interface /
Unification Module (http://opium.sourceforge.net/). This package allows you to generate files in
.recpot format using the latest pseudopotential generation technology.
Besides changing the global selection of pseudopotentials, it is possible to change the individual
selections for each element according to the selected value of the exchange-correlation functional.

Tip: Individual selections are also useful for elements such as oxygen and silicon where additional soft
versions of the USPs are available. These require a smaller energy cutoff but may be less transferable
than the standard potentials.
Nonlinear core corrected pseudopotentials

USPs with nonlinear core correction (NLCC) are provided for some elements, most notably transition
metals. These potential files have a .uspcc extension. In some cases, NLCC potentials are more
accurate than the corresponding non-corrected USPs and others they provide a cheaper and less
accurate alternative to the non-corrected USPs.
You can distinguish between these two cases by comparing the Valence values displayed on the
Potentials tab of the CASTEP Electronic Options dialog.
For example, Mn_00.usp and Mn_00.uspcc both use seven valence electrons. This means that the
NLCC version is more accurate (and it is therefore the default potential for Mn). On the other hand, Cr_
00.usp uses 14 valence electrons, while Cr_00.uspcc uses only six. This means that Cr_00.usp
treats semicore s and p states explicitly as valence states and is thus more accurate than the NLCC
version.
To change global pseudopotential selection
1. Choose Modules | CASTEP | Calculation from the Materials Studio menu bar.
2. Select the Electronic tab.
3. Set the Pseudopotentials option to either Ultrasoft or Norm-conserving using the dropdown list.
To change pseudopotential selection for a given element
3. Click the More... button to open the CASTEP Electronic Options dialog.
4. Select the Potentials tab.
5. Set the Pseudopotential for each element from the dropdown list which appears in the appropriate
grid cell when it is edited (for example, for Mg the following pseudopotentials would be available
Mg_00.usp, Mg_00PBE.usp, Mg_00PW91.usp, Mg_00.recpot).
6. Click the View button to display the selected pseudopotential scheme.
Pseudopotential database
Pseudopotentials are stored as ASCII text files in the folder
share\Resources\Quantum\CASTEP\Potentials. The headers of these files contain useful information
about:
Recommended cutoff energies for different convergence levels
Pseudopotential generation data (core radii, electronic configuration, exchange-correlation potential,
and so on)
Convergence testing (energy and forces on atoms for a simple system as a function of the energy
cutoff)
Scientific testing (lattice constants and molecular bond lengths compared to experiment)
This information might be useful when deciding which potential to use, or when writing up the results of
a calculation. In addition, core radii can be used as a guide to selecting a real-space transformation
radius.

Setting up the basis set

Energy cutoff
The basis set, as defined by the energy cutoff value, is one of the most important parameters that
determine the accuracy (and the cost) of a CASTEP calculation. The easiest way to set this value is by
using the Energy cutoff option on the Electronic tab of the Calculation dialog. If you use this method,
the cutoff value which is optimal for a given level of the total energy convergence will be determined,
based on the information in the pseudopotential data files.
Alternatively, you can specify a custom energy cutoff value on the Basis tab of the Electronic Options
dialog. Custom energy cutoffs may be required in a number of cases, for instance, when modeling a
molecule-surface interaction, for example CO on a Pt surface. In such situations, the protocol for the
calculation of the binding energy includes separate CASTEP runs for the isolated molecule, the clean Pt
surface and finally the CO-Pt complex. The basis sets for the systems containing oxygen will be
determined by the convergence properties of the oxygen potential, the hardest element out of O, C,
and Pt. In order to achieve maximum error cancellation, it is necessary to set the energy cutoff for the
clean Pt surface calculation to the same value as in the other two runs. Therefore, an automatic
selection of the energy cutoff is not totally appropriate in this case.
To change the energy cutoff quality
3. Set the Energy cutoff quality using the dropdown list.
4. The energy cutoff value that corresponds to the selected quality is displayed next to the dropdown
list.
To set a specific energy cutoff value
3. Click the More... button to access the Electronic Options dialog.
4. Select the Basis tab.
5. Check the Use custom energy cutoff option.
6. Modify the energy cutoff value.
FFT grid
The size of the FFT grid which is used to represent wavefunctions, charge density and potentials is
determined by the energy cutoff value and the reciprocal lattice vectors.
The ideal FFT value is determined by the requirement that there be no wrap-around error in the
representation of wavefunctions and potentials (Payne et al., 1992).
This value corresponds to the maximum G-vector of the FFT grid, Gmax, which is exactly twice the radius
of the reciprocal space sphere determined by the energy cutoff Ecut.
However, it is possible to use smaller FFT values and still obtain accurate answers even though some
wrap-around error will be present. By default CASTEP uses a grid that corresponds to 3/4 of the ideal
grid size. This setting can be changed using the Derived grid option on the Basis tab of the Electronic
Options dialog. The actual values of the FFT grid are then displayed in the Divisions text boxes on the
same dialog.

Note: Ultrasoft potentials require a better FFT grid in order to represent the augmentation density
accurately. The PW91 exchange-correlation functional also requires a better grid, to represent
gradient-dependent terms in the potential.
Therefore, CASTEP derives a finer FFT grid in both of these cases, compared with other exchange-
correlation functionals or norm-conserving potentials.
The table below shows the factor by which the actual grid differs from the ideal one depending on (i)
Derived grid setting and (ii) the use of either the PW91 functional or ultrasoft pseudopotentials.
Standard Fine Precise

No USP, no PW91 0.75 0.875 1.0
Either USP or PW91 0.875 1.0 1.15
Tip: Use the Fine setting (or better) for high-accuracy calculations, especially when the cell
optimization is required.
To change the FFT grid quality
3. Click the More... button to access the Electronic Options dialog.
5. Set the Derived grid quality from the dropdown list.
6. The FFT grid values that corresponds to the selected quality are displayed below the dropdown list.
Finite basis set corrections
It is recommended that you apply a finite basis set correction to the total energy and to the stress
tensor when stress is calculated, including geometry optimization runs with variable cell parameters and
NPT/NPH molecular dynamics calculations. The Apply finite basis set correction setting corresponding to
this is Smart.
Note: Variable cell CASTEP calculations can be carried out in two modes, either fixed basis set quality
(that is, fixed energy cutoff), or fixed basis set size (fixed number of plane waves). Finite basis set
correction is required only in the former case, and this is accounted for automatically when the Smart
setting is used.
CASTEP calculates the correction by determining the total energy at a number of cutoff energies, then
evaluating the derivative required in the correction term, numerically. It is normally sufficient to use
three reference points in such calculations.
In some cases the value of the derivative may be known from a previous calculation. In such
circumstances, the value can be input directly, using the Manual Correction mode.
However, under normal circumstances, it is strongly recommended that the finite basis set correction
settings are left at their default values. These are:
Apply correction: Smart
Correction mode: Automatic
Numerical differentiation: 3 points

Setting up k-points
The k-point set used in a calculation defines the accuracy of the Brillouin zone sampling. The Monkhorst-
Pack k-points used in CASTEP are characterized by divisions along three reciprocal space axes and by an
optional origin shift. However, the origin shift should not be used. Thus, the k-points setup procedure
simply involves selecting three integer divisions.
The quality of the k-point set can be quantified in a number of ways; CASTEP uses the distance between
the points in reciprocal space as a numerical measure. The simplest way to define the set is the
following:
Simple way of setting the k-points
3. Choose the desired k-point set from dropdown list.
This method creates either a Monkhorst-Pack set of the selected quality (Coarse, Medium, or Fine) or
instructs CASTEP to use only one Γ-point (the origin in reciprocal space).
Note: Explicit selection of Γ-point sampling is not recommended. CASTEP will automatically use this
option if the cell is very large in real space, so that the Brillouin zone is small and no sampling is
required.
In all other cases, the Γ-point is the least representative of all Brillouin zone points and using it as the
only sampling point can distort the results severely.
Puska (2000) showed, for example, that there is a 1-2 eV error in the vacancy formation energy in
silicon when the Γ-point is used for cells containing up to 128 atoms.
Finer control over k-point sets can be exercised by using the k-points tab on the CASTEP Electronic
Options dialog. This tab allows you to enter the actual Monkhorst-Pack mesh parameters by selecting
the Custom grid parameters option.
CASTEP automatically optimizes the mesh parameters according to the point group symmetry of the 3D
model. For example, in a cubic crystal the even mesh parameters, N, will generate the set with as many
k-points as the one with the odd mesh parameters, N-1. Since the former set provides better sampling,
it will be selected automatically when either Quality or k-point separation is used to define the k-point
set. Custom grid parameters is the only option which allows you to specify a suboptimal mesh with odd
divisions.
The quality of the k-point sampling is particularly important for metallic systems, where rapid changes in
electronic structure may occur along the energy band that crosses the Fermi level. Insulators or
semiconductors, even when they are treated using variable occupation numbers for electronic states,
are less sensitive to the quality of k-point sampling. The default settings used by CASTEP are designed to
give accurate sampling for metallic systems. This means that you can get good results for insulators and
semiconductors with a slightly less fine k-point mesh than the default.
Note: The total energy is not guaranteed to decrease as more k-points are added. Therefore, when
carrying out convergence testing, you should strive to find a set of k-points such that further
improvements do not alter the total energy beyond the tolerance level you require. However, the
energy is not likely to converge smoothly and oscillations are to be expected.
Setting up SCF parameters

SCF settings determine the algorithm that CASTEP uses to find the ground state of the electronic
subsystem, as well as the accuracy required. Most of these settings do not need to be changed by the
user. For example, the SCF tolerance is controlled by the global Quality option on the Setup tab. It can

also be modified using the SCF tolerance option on the Electronic tab, however this is not
recommended.
Similarly, the maximum number of SCF cycles, which can be adjusted using Max. SCF cycles option on
the SCF tab on the CASTEP Electronic Options dialog, need not be changed under normal circumstances.
The Max. SCF cycles setting determines how many SCF steps are taken by CASTEP before it moves
atoms according to the task being performed (that is, Geometry Optimization or Dynamics).
Note: The CASTEP server automatically increases the number specified in the interface by a factor of
three for metallic systems.
Electronic minimization algorithm

The algorithm that is used to solve the DFT equations is specified by the Electronic minimizer option on
the SCF tab on the CASTEP Electronic Options dialog.
Density mixing is the recommended choice, in terms of both robustness and efficiency. It is 2-4 times
faster for insulators than the conjugate-gradient based All Bands/EDFT scheme. The Density mixing
scheme is especially good for metallic systems, where speedups for metal surfaces compared to
conjugate gradient schemes are in the region of 10-20.
The only case where density mixing may not improve performance is for molecule in a box calculations.
The default density mixing settings use Pulay mixing and conjugate-gradient minimization of each
electronic state. You should only attempt to change these parameters if SCF convergence is very poor.
Sometimes it helps to reduce the length of the DIIS history from the default value of 20 to a smaller
value (5-7). It might also be helpful to decrease the mixing amplitude from the default value of 0.5 to 0.1-
0.2.
Variable electronic states occupancies
By default CASTEP uses variable electronic occupancies, thus effectively treating all systems as metallic.
This is recommended, as it speeds up density mixing optimization, even for systems with large band
gaps. The number of empty bands should be sufficiently large to cater for nearly degenerate bands close
to the Fermi level. This is relevant for transition or rare earth metal compounds, where narrow d or f
bands can be pinned at the Fermi level.
If the number of bands used for such a system is insufficient, the SCF convergence will be very slow and
probably oscillatory. Occupation numbers of the highest electronic states as reported in the .castep
file are likely to be noticeably nonzero for at least some k-points.
SCF convergence with the Density mixing minimization scheme can sometimes be poor for metallic
systems. If this is the case, the alternative All Bands/EDFT scheme, which is based on the ensemble
density-functional theory (Marzari et al., 1997) offers a more robust alternative.
Tip: Slow SCF convergence is often indicative of an insufficient number of empty bands, especially in
spin-polarized calculations. To check if this is the cause, inspect the occupancies of the highest energy
electronic states. They should be very close to zero for all k-points in a calculation which is setup
correctly.
Dipole corrections
By default CASTEP does not perform dipole corrections, however, for slab and single molecule systems
with P1 symmetry either a Self-consistent or Non self-consistent dipole correction can be applied. The
self-consistent scheme is based on the method suggested by Neugebauer and Scheffler (1992) where the
correction potential is recalculated at each SCF step. The non self-consistent scheme is based on the
approach of Yeh and Berkowitz (1999) where a dipole correction is added after the SCF has converged. In

this scenario only the total energy and its gradients are corrected, not the electrostatic potential. As a
result, this type of correction is not suitable for electrostatic potential studies such as workfunction
calculations.
Dipole corrections can be essential in eliminating nonphysical electrostatic interactions between periodic
images, improving accuracy of calculated adsorption energies for molecules on surfaces, for example.
Tip: It is recommended to use the All Bands/EDFT electronic minimization scheme when applying a
self-consistent dipole correction to an elongated cell of a slab representing a metal surface; the
Density mixing minimization scheme may fail to converge for such systems.
Setting up a geometry optimization

Geometry optimization is one of the tasks most often performed with CASTEP.
Convergence criteria
The accuracy of the calculation is controlled by the Quality option on the Geometry Optimization dialog.
For a detailed description of the quality settings please refer to the Setting the quality of a calculation
topic.
Geometry optimization algorithm
The BFGS algorithm is the recommended algorithm for minimizing structures. The damped molecular
dynamics approach is always slower and does not allow cell relaxation. The only case when damped
dynamics may be appropriate is in systems with a very flat potential energy surface. BFGS can be
extremely slow in such cases and can get stuck in a local minimum.
interface plane).
Constraints
Geometry optimization in CASTEP obeys constraints on fractional atomic positions imposed using the
Materials Visualizer. You can set such constraints using the Edit Constraints dialog, accessible from the
Modify menu. Note that atoms must be completely fixed; CASTEP does not support partial constraints
on the x, y, and z components of Cartesian atom positions.
Tip: At present, you must check the Fix fractional position checkbox on the Atom tab of the Edit
Constraints dialog in order to apply fixed atom constraints in CASTEP. This has the effect of fixing both
fractional and Cartesian positions in a fixed cell calculation, and fixing fractional positions in a variable
cell run. In the current version of Materials Studio, checking the Fix Cartesian position checkbox has
no effect on CASTEP calculations.
More general linear constraints in CASTEP can be specified manually by editing the .cell file.
Note: The default setting in CASTEP is to optimize atomic coordinates only. You must choose an
option from the Cell optimization dropdown list on the Minimizer tab of the Geometry Optimization
dialog if cell optimization is required.
Non-linear constraints
Geometry optimization using delocalized internals in CASTEP obeys constraints on interatomic
distances, bonds, and/or torsions imposed using the Materials Visualizer. You can set such constraints

using the Edit Constraints dialog, accessible from the Modify menu.
Notes:
All non-linear constraints are only taken into account if you choose the delocalized internal
minimizer, by checking the Use delocalized internals checkbox on the Options tab of the CASTEP
Geometry Optimization dialog.
The Damped MD algorithm for geometry optimization acknowledges only constrained bonds
(distances) between atoms, all other constraints (torsions and angles) are ignored.
Non-linear constraints cannot be applied in conjunction with symmetry constraints. Thus, if your
crystal has symmetry other than P1, you will be prompted to convert the crystal symmetry to P1
before you can continue.
Non-linear constraints cannot currently be applied to disordered systems.
Potential pitfalls
One of the most difficult parts of geometry optimization in CASTEP is cell optimization. It is important to
ensure that you use a finite basis set correction in such calculations, and preferably a fine quality level.
The accuracy of the stresses which are used in the cell optimization algorithm are crucial for the success
of geometry optimization. Certain systems, for example, rare-earth compounds with highly localized
electronic states, require very stringent criteria for SCF convergence in order to converge the stress
tensor. This is particularly true for the Density mixing minimizer.
If cell optimization fails with the following message in the output file:
"BFGS: Geometry optimization failed to converge after ... steps",
You should try one of the following:

change electronic minimization algorithm to All Bands/EDFT scheme
use a stricter SCF tolerance
use a less strict Max. stress tolerance
Another potential pitfall is the use of the Fixed Basis Size Cell optimization setting when the starting
geometry is very different from the final one. Finite basis set correction does depend on the cell
variables, although this dependence is disregarded by the minimizer. In addition, the effective cutoff
energy changes when the cell geometry is modified with the above setting (it is the number of plane
waves that is kept fixed). If this change takes the dEtot/d(ln Ecut) function far away from the point that
was used to evaluate the finite basis set correction, the results obtained will not be accurate. Therefore,
you should compare the starting and final geometries and perform a completely new run starting from
the final configuration if the difference between the two is large.
Tip: Fixed Basis Quality is a recommended setting for cell optimization. Even then it is a good idea to
perform an additional geometry optimization calculation after successfully completing the first,
particularly if there were noticeable changes in the geometry.
Setting up a molecular dynamics calculation

In most cases a dynamics calculation is preceded by structure minimization. It may also be desirable to
perform minimizations after the calculation on several of the conformations that were generated.
Note: CASTEP dynamics calculations can be only performed for systems with P1 symmetry.

Defining the time step

A key parameter in the integration algorithms is the integration time step. A common rule-of-thumb
used to pick the time step is that the highest frequency vibration should be sampled between 15 and 20
times in one cycle. For example, if the highest frequency is 20 THz, a typical optical mode frequency in an
insulator, a time step of 2.5-3.3 fs is appropriate (period = 1/frequency = 50 fs). In water, the stretch
frequencies are around 110 THz, indicating that a time step of 0.45-0.6 fs is required. You will probably be
able to use a time step that samples the motion as few as 10 times in a cycle. However, you must check
your choice of time step by monitoring energy conservation in the NVE ensemble. A thermostat in the
NVT ensemble can completely mask inadequate integration.
Note: The Time step can be increased to about 4-5 fs when the extended Lagrangian formulation
(Steneteg 2010, Niklasson, 2011) is used.
To choose a time step
3. Click the More... button to open the Dynamics dialog.
4. Select the Dynamics tab.
5. Set the Time step in the text box.
Note: Along with the related value Number of steps, Time step also determines the Total simulation
time. Changes to the Dynamics time also affect the Number of steps.
Choosing an ensemble
You can control temperature of a CASTEP dynamics calculation, in order to simulate a system that
exchanges heat with the environment. Under these conditions, the total energy of the system is no
longer conserved and extended forms of molecular dynamics are required.
You can simulate several thermodynamics ensembles with a constant number of particles.
Ensemble Conditions Description
NVE Constant- The Newtonian equations of motion, which conserve the total
volume/constant- energy, are used. The unit cell is fixed.
energy dynamics The temperature is allowed to vary. Energy is the constant of motion
- it can fluctuate slightly, but there should be no systematic drift.
NVT Constant- The unit cell is fixed. A thermostat maintains a constant temperature.
volume/constant- The dynamics are modified to allow the system to exchange heat
temperature with the environment at a controlled temperature. Several methods
dynamics of scaling or controlling the temperature are available.
NPH Constant- The size of the unit cell is allowed to vary with a barostat to maintain
pressure/constant constant pressure. The enthalpy is a constant of the motion.
enthalpy dynamics The size of the unit cell is allowed to vary, while the temperature is
also allowed to vary. The enthalpy, which is a constant of the motion,
is not allowed to vary beyond a set value between dynamics steps.
NPT Constant- The size of the unit cell is allowed to vary with a barostat to maintain
pressure/constant- constant pressure. A thermostat maintains a constant temperature.

Ensemble Conditions Description

temperature Similar to NPH, except that temperature is controlled. Several
dynamics methods of scaling or controlling the temperature are available.
To choose an ensemble
3. Click the More... button to open the Dynamics dialog.
4. Select the Dynamics tab.
5. Select the required ensemble from the Ensemble list.
6. Select the Options tab to enter parameters for the selected ensemble.
Constraints
Molecular dynamics in CASTEP obeys constraints on atomic positions and/or interatomic distances
(bonds) imposed through the Materials Visualizer. You can set such constraints using the Edit
Constraints dialog, accessible from the Modify menu.
To fix atomic positions in CASTEP you must check the Fix fractional position checkbox on the Atom tab
of the Edit Constraints dialog.
Setting up a transition state calculation

CASTEP transition-state searches are performed using synchronous transit methods. These work best in
situations where the structures of the reactants and products are known, but the location of the
transition state is not.
A transition-state search requires a trajectory document (for example, an .arc or .xtd file) as input.
The reactants are taken from the first frame of the trajectory, and the products from the last frame. For
quadratic synchronous transit (QST) calculations, the current frame is used for the QST mid-point. The
trajectory files generated by any of the other transition state search methods may be used as input to a
QST run.
Note: When a transition state search is performed on a periodic system the unit cell is fixed.
topic.
Note: Synchronous transit calculations are performed in Cartesian coordinates. There is no option to
override this.

To set up a synchronous transit calculation

1. Begin by constructing two separate documents, one for the reactants and a second for the
products.
2. Determine the correspondence between atoms in the two documents using the Find Equivalent
Atoms tool. The synchronous transit method performs a geometric interpolation between the
atomic coordinates of the atoms in the reactants and the atoms in the products. In order to
accomplish this, it is necessary that the program understand which atom matches to which.
3. Generate a trajectory that converts reactants into products using the Reaction Preview tool. You
can animate this document to check that the reactants are converted correctly to products. If you
are satisfied with the match, proceed with the calculation. If not, use the Find Equivalent Atoms tool
to edit the atom correspondence and try again.
4. Using the document that was created by the Reaction Preview tool, select your options for the TS
Search calculation and submit the CASTEP calculation by clicking the Run button.
Tip: To optimize the reactant and product structures as part of the TS Search run, check the Optimize
reactants and products checkbox on the CASTEP Transition State Search dialog.
Setting up a transition state confirmation calculation

The LST and QST tools locate a maximum energy structure along the reaction path, but this maximum
may not, in fact, be the transition state that you are looking for. You can use the TS confirmation tool to
confirm that the transition state found does indeed connect your presumed reactant and product.
A TS confirmation calculation requires three structures to proceed - the reactants, the products, and the
transition state. The trajectory used as input for this calculation should contain reactants in the first
frame and products in the last frame. Transition state structure is taken as the current frame of this
trajectory, unless the current frame is either the first or the last - in which case the penultimate frame is
used as transition state. This is the frame where CASTEP TS Search calculations store the transition state
determined in the synchronous transit search.
To perform a Transition State Confirmation
1. First perform a TS Search using LST or QST. The trajectory computed by this method is used as
input to the TS Confirmation. Make sure this trajectory document is in focus when you set up the
TS Confirmation.
3. Open the Setup tab.
4. Set the Task to TS Confirmation.
5. If desired, set additional options by selecting the More... button to open the CASTEP TS
Confirmation dialog. Normally, the default options will yield adequate results.
6. Click the Run button.
Note: The Max. images is the upper limit for the number of frames. Structures that are too similar will
be dropped during the calculation.
Users should be aware that TS Confirmation jobs can take a long time to complete. These jobs perform a
series of geometry optimizations along the reaction pathway, requiring quite a lot of computer time.
Tip: At the end of the calculation, you can select any geometry on the reaction pathway using the
chart/trajectory tools and perform subsequent calculations. In this way you could, for example,
perform further geometry optimization on an interesting structure.

Setting up an elastic constants calculation

In most cases the calculation of elastic constants is proceeded by full geometry optimization, including
cell optimization. This means that elastic constants will be generated for the theoretical lattice
constants. However, it is possible to skip this step and generate elastic constants for the experimental
structure.
Elastic constants are evaluated by calculating the stress tensor for a number of distorted structures.
Internal coordinates are optimized in each run, while keeping the lattice parameters fixed. The accuracy
of the elastic constants depends to a great extent on the accuracy of the SCF part and also on the level
of convergence of geometry optimizations for each distorted structure.
Setting up strain patterns

CASTEP generates the strain patterns automatically, based on the lattice type of the structure. The
maximum number of patterns required is six for a monoclinic structure, while one pattern is sufficient
for cubic cells. Certain symmetries allow you to modify the patterns so that whenever possible, volume-
conserving strains are generated.
The quality of the calculated values depends strongly on the amplitude of the applied distortions and
the number of points that are used for each strain pattern. You should use at least four steps for each
strain to obtain a statistically reliable linear fit of the stress-strain relationship. The maximum strain
amplitude should be chosen so as to be (i) sufficiently low that the material stays within the linear
elasticity regime, and (ii) sufficiently high that the distortion generates stresses significantly higher than
the error level of the CASTEP calculation (errors due to imperfect SCF convergence, for example).
To set up strain patterns
3. Choose the Elastic Constants task.
4. Click the More... button to open the CASTEP Elastic Constants dialog.
5. Select the Elastic Constants tab.
6. Specify the Number of steps for each strain and Maximum strain amplitude in the appropriate text
boxes.
Convergence criteria
The accuracy of the calculation is controlled by the Quality setting on the Minimizer tab of the CASTEP
Geometry Optimization dialog.
topic.

To change the convergence tolerances

3. Choose the Elastic Constants task.
4. Click the More... button to open the CASTEP Elastic Constants dialog.
5. Select the Options tab.
6. Specify the Quality using either the dropdown list or by providing individual convergence tolerances
for the energy, maximum force and maximum displacement in the corresponding text boxes.
Note: For trigonal symmetry, the orientation standard where C lies along the z-axis and A is in the xz
plane must be used. For further details on the lattice orientation standard and how to set it, see the
Viewing or changing the lattice parameters topic.
Setting up a DFT+U (LDA+U) calculation

CASTEP DFT+U calculations are only available in the spin-polarized mode, even if there is no magnetic
solution. The majority of correlated systems are either ferrimagnetic or anti-ferromagnetic, so the initial
spin moments must be carefully chosen (see Changing atomic spin). In some cases, a supercell must be
constructed before beginning calculations.
Note: The DFT+U formalism is not compatible with NMR, phonon, or polarizability calculations. The
formalism cannot be used with mixture atoms or real-space pseudopotentials.
To set up a DFT+U calculation
1. Either import a structure from a pre-existing file or construct a new molecule using the sketching
tools in the Materials Visualizer.
2. Select Modify | Electronic Configuration from the menu bar to display the Hubbard U tab of the
Electronic Configuration dialog.
3. Set the U values for the orbitals as desired (see Changing Hubbard U values for further guidance).
Note: Default effective Hubbard U values should be considered as guidelines only, as they are
not universal and depend greatly on the chemical environment. The results obtained depend on
the value of U as well as the atomic orbitals, so literature values are often inappropriate.
4. On the Spin tab set the Formal spin parameters for your system. Then close the Electronic
Configuration dialog.
7. Select a Functional from the dropdown list (see the theory section for more information on
functionals).
8. Check the Spin polarized and Use DFT+U checkboxes.
The symmetry used in DFT+U calculations is often lower than the crystallographic symmetry, so the
number of k-points needed is increased. More calculations are carried out at each step increasing
computation times and requiring more steps to achieve convergence.
Tip: For cubic systems, converting to tetragonal or rhombohedral symmetry may improve
performance.

Note: Sometimes the density mixing scheme may not converge. In such cases you should switch to
an EDFT minimizer to improve results and set the option to Optimize total spin after 1 SCF step.
Note: The Hubbard U operator can be applied only to the states which have an LCAO projector in the
pseudopotential. If there is no projector for any orbital with nonzero U value, CASTEP will return the
following error message:
Hubbard U is requested for the states which do not have LCAO
projectors. Please check HUBBARD_U block in the cell file.
If you think that the states to which you want to apply Hubbard U are really important, you could use
a different pseudopotential (on-the-fly generated potentials are likely to have more projectors than
other pseudopotentials).
Setting up a core hole calculation

Calculations with core holes are designed to describe the electronic structure of a system containing
highly exited ions with a hole in a core shell. Such calculations can be relevant to the description of such
excitations and relaxations of these excited states.
Core holes can be used in any CASTEP calculation, however they are most relevant to the generation of
core level spectroscopy results. It is not recommended to carry out geometry optimizations in the
presence of core holes.
Note: CASTEP calculations using core holes are only available for atoms using on-the-fly generated
pseudopotentials (OTFG).
To set up a core hole calculation
1. Either import a structure from a pre-existing file or construct a new structure using the sketching
and crystal building tools in the Materials Visualizer.
2. Extend the crystal lattice using the Supercell or Redefine Lattice dialog and convert to the primitive
representation.
3. Convert the symmetry of the crystal to P1, to prevent core holes being placed on symmetrically
equivalent atoms.
4. Select Modify | Electronic Configuration from the menu bar to display the Core Hole tab of the
Electronic Configuration dialog.
5. Set up the core hole(s) in the structure as desired (see Changing Core Hole values for further
guidance). Close the Electronic Configuration dialog.
6. Open the Find Symmetry dialog and select the Options tab. Check the CoreShellWithHole checkbox
in the list of properties. On the Find tab click the Find Symmetry button then the Impose Symmetry
button.
7. Choose Modules | CASTEP | Calculation from the menu bar to open the CASTEP Calculation dialog.
8. On the Electronic tab check the Use Core Hole checkbox.
9. Select On the fly from the Pseudopotentials dropdown list.
Note: To prevent interactions between periodic images of core hole sites sufficiently large supercells
might be necessary.

Note: CASTEP calculations with core holes assume by default that an electron is removed from the
system, so it is treated as having a charge of 1 (or one more than specified in the Charge field on the
Setup tab of the CASTEP Calculation dialog). In some circumstances, for example when studying
impurities, it might be more appropriate to consider the system as charge neutral. In order to achieve
this you should specify the Charge of -1 on the Setup tab, in this way the CASTEP input file will have a
zero charge. It is also possible to edit the seedname.param file to specify a fractional charge. The
strength of the core hole can be adjusted by editing the seedname.cell file and modifying the
pseudopotential definition string (for example, change {1s1} to {1s0.5} to use a core hole with
the charge of 0.5).
Setting up a work function calculation

The work function is the minimum energy (usually measured in electron Volts) required to remove an
electron from a solid to a point immediately outside the solid surface (or the energy needed to move an
electron from the Fermi energy level into a vacuum). This energy depends on the orientation of the
crystal, different crystallographic surfaces have different work function values. The typical range of
values of work function for all crystalline elements is from 2 to 6 eV, and the orientational dependence of
the work function is of the order of 1 eV.
A practical way of evaluating work function is to compare the values of the Fermi energy and that of the
electrostatic potential in a vacuum away from the surface. CASTEP calculations for crystal surfaces are
carried out on slabs with a region of vacuum. Effectively, an infinite array of 2D-periodic slabs of material
is separated by wide vacuum spacings. CASTEP produces the Fermi energy for such systems, and the
spatial distribution of the electrostatic potential. Materials Studio averages the electrostatic potential in
the planes parallel to the surface. This approach allows the value of electrostatic potential in vacuum,
and hence the work function, to be determined.
The work function can have a large dependence on the crystal structure and surface orientation. It is
recommended that the structure is carefully prepared before calculation of the work function, as
described in the steps below. The recommended sequence of steps includes the geometry optimization
of the bulk structure, preparation of the surface followed optionally by optimization of atomic
coordinates in the surface and bulk layers. It is possible to perform work function calculations without
this optimization, so that the effects of surface relaxation on the work function can be investigated. It is
reasonable to keep the structure of the middle of the slab as close to the perfect bulk structure as
possible, for example by imposing fixed atom constraints on some inner atoms of the slab.
It is important to have a fair representation of the bulk material, by including at least 8-10 Å of material
in the slab calculation. It is equally important to provide enough vacuum between layers of materials so
that the electrostatic interactions between two sides of a slab are negligible and electrostatic potential
reaches its asymptotic value; there should be at least 30 Å of vacuum in the cell.

To set up a work function calculation

1. Either import a structure of the bulk material from a pre-existing file or construct a new structure
using the sketching and crystal building tools in the Materials Visualizer.
2. Geometry optimize the bulk structure using CASTEP.
3. Cleave the required crystallographic surface using the Cleave Surface dialog so that the thickness
provides a meaningful representation of the bulk.
4. Build a slab using the Build Vacuum Slab Crystal dialog, you should ensure that the distance
between the surface and the end of the vacuum is great enough that there can be no potential
interactions between the surface and the next layer.
7. Choose the Geometry Optimization task.
8. Fix fractional atomic positions of some atoms in the middle of the slab using the Edit Constraints
9. Select either the LDA or GGA Functional from the dropdown list (see the theory section for more
information on functionals).
11. Follow the steps in the Displaying the averaged potential chart for work function calculations topic.
The result of this procedure is a chart of the electrostatic potential as a function of position along the
surface normal, with Fermi energy and the vacuum energy level marked as two horizontal lines. The
work function value is reported in the chart caption.
Setting up a reaction kinetics calculation

Information generated by CASTEP as part of the transition state search task enables you to predict the
reaction rate coefficient of a chemical reaction. The algorithm is based on transition state theory and
involves evaluation of the partition functions of reactant(s), product(s), and transition state. Calculation
of a partition function involves obtaining the vibration spectra, this in turn is calculated from the Hessian
matrix.
The reaction rate calculation requires three main ingredients:
1. Transition state search, performed after optimizing geometry of reactants and products
2. Calculation of the Hessians for all the reaction species
3. Calculation of the partition functions and reaction rates for forward and reverse reactions
Transition state searching in CASTEP can be performed using either the LST or QST formalism. To
optimize the reactant and product structures as part of the TS Search run, check the Optimize reactants
and products checkbox on the CASTEP Transition State Search dialog. It is important to set constraints
correctly in the initial documents - this has effect both on the cost of the subsequent calculations, and
on the accuracy of the results obtained.
To calculate the Hessians for all the reaction species you should check the Calculate partition functions
checkbox on the CASTEP Transition State Search dialog. This setting causes vibrational frequencies to be
evaluated for reactant, product, and transition state structures. A partial Hessian will be used if there are
constrained atoms in the system. Since the calculations rely on finite displacements, the cost can be
reduced significantly by fixing coordinates of substrate atoms that are not involved in the surface
reaction itself.

The result of the transition state search is an 3D Atomistic Collection Document containing reactant,
product, and transition state structures. You can select the "TS" physical system and use the Vibrational
Analysis tool to verify the nature of the imaginary mode associated with the reaction.
Note: The reaction rate coefficient can be calculated only if the transition state has exactly one
imaginary frequency with its eigenvector along the reaction path.
The 3D Atomistic Collection Document generated will contain all the necessary information to perform
the reaction rate calculation itself.
To set up a reaction kinetics calculation
1. Prepare two documents containing reactant and product structures. Set any necessary fixed atom
constraints (fixed atoms should be present in both documents and should have the same
coordinates).
2. Follow the steps required to set up transition state search calculation.
3. Check the Optimize reactants and products checkbox on the CASTEP Transition State Search dialog,
unless you have optimized both structures prior to constructing reaction preview document.
It is recommended to select Ultra-fine for the convergence tolerance for geometry optimization by
changing the task to Geometry Optimization, opening CASTEP Geometry Optimization dialog,
editing convergence settings, and then changing the task again to TS Search. Such an accurate
setting may be necessary to eliminate spurious imaginary modes in the vibrational analysis.
4. Check the Calculate partition functions checkbox on the CASTEP Transition State Search dialog.
5. It is recommended to impose more strict convergence criteria than the default values; lack of
convergence can result in spurious imaginary modes of the transition state itself.
Setting up a calculation on an isolated molecule

CASTEP can be used to calculate the electronic structure and to optimize the geometry of isolated
molecules as well as of solids. In order to study molecules using CASTEP, it is necessary to treat them as
periodic systems by assuming that they are in a box. This can be achieved by creating a supercell
containing the molecule of interest. There is no limitation on the shape of the supercell, but the simplest
approach is to use a rectangular (or even cubic) supercell with a sufficiently large separation between
molecules to eliminate spurious interactions between periodic images.
Since both the properties being investigated and the nature of the molecule itself have an influence on
the degree of molecular separation required, it is not possible to give a definitive distance that should be
established between molecules in a supercell. As a general rule, a box with dimensions that are 4-5 times
the size of the molecule should be sufficient. However, it is still important that you check that the size of
your supercell is adequate by investigating the convergence of the properties you are interested in
against the molecular separation.
Tip: Carrying out a stress analysis is a good way of checking that the molecular separation in a
supercell is sufficient to preclude any interactions between periodic images, since the stress value
provides a guide as to the size of the cell. Alternatively, you could check the band dispersion: the less
dispersion in the valence band, the better the molecular separation in the supercell.
CASTEP is an efficient tool for optimizing the geometry of molecules and also enables you to calculate a
range of molecular properties, including:

Densities of states
NMR shielding tensors and electric field gradients
Vibrational properties
Polarizabilities and IR absorption intensities
Bond and band populations
Note: It is recommended that only the Γ-point is used for electronic calculations on molecular
systems. In addition, the all bands/EDFT electronic minimizer is known to be more efficient for studies
of isolated molecules in supercell geometry than the density mixing minimizer. Therefore, it is
recommended that you change the Electronic minimizer setting to All Bands/EDFT on the SCF tab of
the CASTEP Electronic Options dialog when performing such calculations.
Tip: Calculations for "molecule in a box" systems that do not require geometry optimization can be
sped up if the molecular symmetry is utilized. Use the Find Symmetry tool to find and apply the
symmetry of the molecule to the supercell.
To create a molecule in a box
1. Either import a structure from a pre-existing file or construct a new molecule using the sketching
tools in the Materials Visualizer.
2. Construct a crystal using the crystal building tools in the Materials Visualizer.
3. If your system does not require geometry optimization, find and impose the symmetry of the
system using the Find Symmetry tool in the Materials Visualizer.
Requesting electronic, structural, and vibrational properties

CASTEP can calculate a number of electronic, structural, and vibrational properties, either as part of an
Energy, Geometry Optimization, or Dynamics calculation, or during a separate Properties run.
Note: In the descriptions below, it is assumed that properties are being requested as part of another
CASTEP calculation. It is also possible to request properties separately after a CASTEP calculation has
been carried out. This is done using the Properties option, available under Tasks on the Setup tab.
The procedures used to determine properties in this way are identical to those described below but
additionally, the output files from a suitable SCF run must be available in the appropriate local Project
directory.
Multiple properties can be requested when the CASTEP job is setup. The properties are calculated
when the Run button (or Run Files button) is clicked.
Tip: The Population analysis checkbox on the Properties tab of the CASTEP Calculation dialog is
checked by default.
Electronic properties data are produced in CASTEP by running separate non-self-consistent calculations.
This means that Band structure, Density of states, Optical properties, and Vibrational properties
calculations will all generate their own set of output files. Population analysis and Stress properties are
calculated as part of the main run. This output can be found in the appropriate .castep file. The
Electric field response is generated either as part of a Vibrational properties calculation, in which case
the output can be found in the appropriate .castep file, or as a separate calculation.
Requesting band structure
Calculating band structure properties produces electronic energies along high symmetry directions in
the Brillouin zone. The standard path for each lattice type is taken from Bradley and Cracknell (1972).

The path can be modified using the CASTEP Band Structure Options dialog. The density of points along
the path, which affects the appearance of the resulting chart, can be controlled by the selection for the
k-point set dropdown list or the approximate k-point separation can be manually specified in the
Separation text box, in Å-1, on the Properties tab of the CASTEP Calculation dialog. Conduction band
states can be included by specifying a nonzero value in the Empty bands text box on the same tab.
Note: You are not required to use the same exchange-correlation functional in the band structure
calculation as in the main calculation. This allows you to select a nonlocal screened-exchange
functional to study the electronic structure after performing, for example geometry optimization with
a variable cell using the GGA functional.
Note: CASTEP does not support the use of nonlocal functionals (screened exchange, exact exchange,
and so on) for ultrasoft pseudopotentials, that is, nonlocal functionals can only be requested if all the
pseudopotentials for the calculation are specified as norm-conserving.
To calculate band structure
2. Select the Properties tab.
3. Check the Band structure option on the Properties list.
4. If necessary, modify the Number of empty bands to include more or less states in the conduction
band.
5. Optionally, adjust the density of k-points along the high symmetry directions by using k-point set
dropdown list.
6. Click the More... button to open the CASTEP Band Structure Options dialog.
7. Click the Path... button to open the Brillouin Zone Path dialog. This dialog allows you to inspect and
modify the Brillouin zone path used for the band structure calculation.
8. On the CASTEP Band Structure Options dialog check the Use separate XC functional for band
structure calculation checkbox to use a nonlocal functional for the electronic structure calculation.
9. Select the alternative Functional you wish to use from the dropdown list.
Requesting core level spectroscopy
Calculating core level spectra produces electronic energies on the Monkhorst-Pack mesh of k-points and
the matrix elements for electronic interband transitions. The CASTEP Analysis dialog can be used to
generate observable core level spectra based on this information. Detailed analysis of the impact of
calculation parameters (k-point set, number of empty bands, and so on) on the accuracy of the spectra
generated can be found in the core level spectroscopy theory topic.
To calculate core level spectra
3. Check the Core level spectroscopy option on the properties list.
4. If necessary, modify the number Energy range above the Fermi level for which you wish to calculate
the spectrum.
5. Optionally, adjust the density of Monkhorst-Pack k-points used for the optical properties
calculation by using k-point set dropdown list.
6. Click the More... button to open the CASTEP Core Level Spectroscopy Options dialog.
7. Select the Core level spectroscopy k-points option you want to use and the Band energy tolerance.

the charge of 0.5).
Requesting density of states

Calculating densities of states produces electronic energies on the Monkhorst-Pack mesh of k-points.
CASTEP can always produce a density of states plot, based simply on the results of the main self-
consistent run. The purpose of a density of states property run is typically to:
use a finer k-point mesh than in the self-consistent run or
include more states in the conduction band
Such calculations are intended to provide a better quality density of states over a larger energy range.
This type of run can be also used to request a partial density of states. The quality of the k-points set is
controlled by the k-point set dropdown list on the Properties tab on the Calculation dialog. Conduction
band states can be included by specifying a nonzero value in the Empty bands text box on the same tab.
Note: You are not required to use the same exchange-correlation functional in the density of states
functional to study the electronic structure after performing, for example geometry optimization with
Note: CASTEP does not support the use of nonlocal functionals (screened exchange, exact exchange,
and so on) for ultrasoft pseudopotentials, that is, nonlocal functionals can only be requested if all the
pseudopotentials for the calculation are specified as norm-conserving.
Note: To obtain representative density of states it is recommended to use a k-point set which is
either the same or finer quality than the one used in the SCF calculations.

To calculate density of states

3. Check the Density of states option on the properties list.
band.
5. Optionally, adjust the density of Monkhorst-Pack k-points used for the density of states calculation
by using k-point set dropdown list.
6. If you would like to generate partial or local densities of states, check Calculate PDOS.
7. Click the More... button to open the CASTEP Density of States Options dialog. This dialog gives you
complete control over setting up the Monkhorst-Pack grid.
8. Check Use separate XC functional for DOS calculation on the CASTEP Density of States Options
dialog if you want to use, for example, a nonlocal functional for the electronic structure calculation.
9. Select the alternative Functional you wish to use from the dropdown list on the same dialog.
Requesting electron density difference analysis
Materials Studio provides the option of generating the electron density difference in two different ways:
Electron density difference with respect to a linear combination of the atomic densities.
Electron density difference with respect to a linear combination of the densities of sets of atoms
contained in the model.
The former option produces a density difference field which shows the changes in the electron
distribution that are due to formation of all the bonds in the system. This object is appropriate for bulk
solids to illustrate the charge redistribution due to chemical bonding.
The latter option generates a density difference field which effectively corresponds only to the formation
of bonds between atoms in different sets and to charge redistribution within the sets that is due to the
presence of other sets. This property is useful to describe such processes as bonding of molecule(s) to
external and internal (for example zeolites) surfaces, or creation of large molecules from smaller
fragments.
Note: Materials Studio supports the calculation of the density difference with respect to the densities
of sets of atoms only for tasks that do not involve changes in atomic geometry. For Geometry
Optimization and Dynamics values of the Task property, you can request this type of density
difference after the run is complete by using the Properties task.

To perform an electron density difference analysis

1. Choose Modules | CASTEP | Calculation from the menu bar to open the CASTEP Calculation dialog.
3. Check the Electron density difference checkbox on the properties list.
4. Use the radio buttons to select the appropriate type of density difference to be created.
5. When density difference with respect to sets of atoms is requested, it is necessary to create at least
one set of atoms in the model. There is a naming convention for sets that are taken into account:
they should have "DensityDifference" as part of the set name. In order to create the sets:
a. Choose Edit | Edit Sets from the menu bar.
b. Make sure that the correct 3D structure document is active.
c. Select the atoms that will constitute the first set.
d. Click the New... button to create a new set.
e. Give the set a name, for example DensityDifference1.
f. Repeat the above steps to create further sets if required.
Note: Multiple sets should be mutually exclusive.
Tip: When only one set with the correct name is present in the structure, Materials Studio assumes
that the rest of the atoms should be treated as a second set. Thus, in the case of a molecule-surface
interaction, it is sufficient to create a single set that comprises all the atoms in the molecule.
Requesting electron localization function

Electron localization function (ELF) provides a useful qualitative description of chemical bonding. CASTEP
can calculate ELF at the end of a run and return the results for volumetric analysis.
To request an ELF calculation
dialog.
3. Check the Electron localization function checkbox in the list of properties.
Requesting electronic excitations (TD-DFT)
CASTEP allows you to calculate electronic excitation energies and the corresponding oscillator strengths
(transition probabilities) using time-dependent density functional theory (TD-DFT). These excitation
energies correspond to the locations of absorption peaks in the optical spectrum of a material and
represent an improvement over Kohn-Sham excitation energies in terms of accuracy. The calculations
are carried out using the Tamm-Dankoff approximation (Hirata and Head-Gordon 1999). Knowledge of
the excitation energies and corresponding transition probabilities allows one to calculate full set of
optical properties.

To calculate TD-DFT optical properties

3. Check the Electronic excitations (TD-DFT) option in the properties list.
4. Check the Calculate energies checkbox to obtain excitation energies.
5. Check the Calculate optical properties checkbox to calculate the transition probabilities which can
be used for analysis.
6. If necessary, modify the number of excitations which should be calculated.
The excitation data will be reported in the <seedname>_TDDFT.castep output file.
In certain applications the lifetime of an excited state can be sufficiently long to justify the need for
geometry optimization of this state; this requires calculation of forces within TD-DFT formalism which is
provided by CASTEP.
To optimize geometry for a particular excitation
3. Check the Electronic excitations (TD-DFT) option in the properties list.
4. Check the Optimize geometry checkbox.
5. Modify the excitation number which should have its geometry optimized.
The optimized structure for the specified excitation will be saved in the <seedname>_TDDFT_
GO.xsd output file.
Limitations of electronic excitation calculations in CASTEP
The current version of CASTEP has a number of limitations related to the TD-DFT calculation of electronic
excitations:
The structure must be an insulator (the Metal checkbox on the Setup tab of the CASTEP Calculation
dialog must be unchecked)
Norm-conserving pseudopotentials must be used (see the Setting up pseudopotentials topic)
Fixed orbital occupancies are required (see the Setting up SCF parameters topic)
Only a Gamma point calculation is allowed, which should be sufficiently accurate for a "molecule in a
box" geometry
LDA+U calculations are not supported
Requesting Fermi surface data
Fermi surfaces are generated from information from CASTEP calculations which is stored in the .bands
output file. In order to ensure that the Fermi surface generated is accurate it is recommended that you
use as many k-points as is computationally viable. Fermi surfaces can be considered as the equivalent to
isosurfaces in reciprocal space.

To generate Fermi surfaces for any CASTEP calculation

2. Select the Electronic tab on the CASTEP Calculation dialog and click the More... button to open the
CASTEP Electronic Options dialog.
3. Select the k-points tab and click the Separation radio button.
4. Specify a value of 0.01 1/Å or less for the k-point separation. This ensures that enough k-points are
used over the entire calculation for generating the Fermi surface data.
To generate Fermi surfaces for a CASTEP calculation with DOS properties
3. Check the Density of states option on the properties list and set the appropriate DOS options.
4. Click the More... button to open the CASTEP Density of States Options dialog.
5. Click the Separation radio button and specify a value of 0.01 1/Å or less. This ensures that enough
k-points are used for generating the Fermi surface data without requiring such fine settings for the
rest of the calculation.
Requesting NMR properties
NMR calculations can generate the shielding tensor and/or electric field gradients for all of the atoms in
the selected system. NMR properties are very sensitive to atomic positions, which makes NMR such a
useful experimental tool for structure analysis. This means that it is highly recommended to perform a
geometry optimization run before the NMR calculation. If the structure of a crystal or molecule under
investigation is obtained from an experimental study, it is advisable to optimize positions of hydrogen
atoms first of all. If the forces on heavy atoms as reported by CASTEP are high (in excess of 1 eV/Å),
complete structure optimization is recommended.
A detailed review of the CASTEP NMR formalism and numerous examples of practical applications are
discussed in Bonhomme et al. (2012).
Note: NMR in CASTEP is part of the separately licensed module NMR CASTEP. NMR calculations can
only be performed if you have purchased this module.
Chemical shielding tensor

The chemical shielding tensor, σ(r), is defined as the ratio between an external applied magnetic field, B,
and the non-uniform induced magnetic field, Bin(r):
The isotropic shielding, σiso, is given by one third of the trace of σ(r). From the symmetric component of
the shielding tensor, the chemical shielding anisotropy, σaniso and the asymmetry parameter, η, can be
defined in terms of the principal components of the shielding tensor:
and:
where:

For values of σaniso close to zero the asymmetry parameter will be ill-defined.
Electric field gradient
The interaction of a quadrupolar nuclei with an external magnetic field can be characterized by the
quadrupolar coupling constant, CQ, and the asymmetry parameter, ηQ. If the principal components of
the traceless electric field gradient tensor are labeled, Vxx, Vyy, and Vzz such that:
then:
where Q is the nuclear electric quadrupole moment, and:
For very small values of Vzz the asymmetry parameter will be ill-defined.
The value of the quadrupolar moment depends on the actual isotope; CASTEP makes a suggestion
based on the most typical isotope used in solid state NMR experiments. The value of Q affects only the
quadrupolar coupling constant, CQ, calculated and printed out by CASTEP. If you find that the wrong
value of Q was used you can rescale the generatedCQ constant using a different Q value.
Note: The list of default values is based on the compilation by Pyykkö (2008). CASTEP versions prior
to the 5.0 release used an older compilation by Harris (1996), so some results for quadrupolar
coupling constants may have changed in later versions.
J-couplings
NMR J-coupling or nuclear spin-spin coupling is an indirect interaction of the nuclear magnetic moments
mediated by the bonding electrons. It is manifested as the fine structure in NMR spectra, providing a
direct measure of bond strength and a map of the connectivities of the system.
Induced magnetization density and current density are expected to be short-ranged. This forms the
basis of using J-coupling as a tool for probing the strength of interatomic bonds. However, in a periodic
calculation the perturbing nucleus can be viewed as similar to a defect in a defect calculation. Hence,
sometimes it might be necessary to construct a supercell which is large enough to inhibit the interaction
between the periodic defects or perturbations. Convergence with respect to the cell size should
represent an important test in establishing accuracy of J-coupling calculations in either periodic systems
or in molecule in a box calculations.
Note: J-coupling can be calculated only for non-magnetic systems. J-coupling calculations are
supported only for systems with P1 symmetry. If your crystal has symmetry other than P1, you will
be prompted to convert the crystal symmetry to P1 before you can continue.

To calculate NMR properties

2. Choose the Electronic tab on the CASTEP Calculation dialog and select On the fly from the
Pseudopotentials dropdown list.
3. On the Properties tab, check the NMR option on the list of properties.
4. Select the properties you wish to determine:
Shielding
EFG
J-coupling
G-tensor
5. Choose the method you wish to use to determine the NMR properties from the System type
dropdown list (Crystal, Molecule, or Auto). The Molecule option refers to the supercell description
of isolated molecules.
6. If J-coupling is selected, then there are some requirements:
At least one atom in the system must be selected, J-couplings will be calculated between the
selected atom(s) and all other atoms in the system
On-the-fly-generated pseudopotentials must be used
The Relativistic treatment of the on-the-fly-generated pseudopotentials (on the Electronic tab
of the CASTEP Calculation dialog) must be set to either Schroedinger for non-relativistic
treatment or ZORA for scalar-relativistic effects to be taken into account.
Note: NMR parameters will be calculated only for the elements for which the on-the-fly-generated
pseudopotentials are chosen.
Tip: It is not recommended to use PW91 exchange-correlation functional when requesting NMR
properties. PW91 functional may result in sharp real-space features of on-the-fly-generated
pseudopotentials; PBE, RPBE, WC, BLYP, or PBESOL are better options when a GGA functional is
required.
EPR G-tensor
Electron Spin Resonance (EPR - also known as Electron Paramagnetic Resonance) is a powerful
experimental probe of the structure of defects in solids. EPR spectra of spin ½ centers are made up of
two contributions:
the hyperfine parameters
the g-tensor
The g-tensor arises from the interaction of the electronic spin with external magnetic field. This term
plays a somewhat similar role to the shielding in NMR; induced electronic currents in the sample modify
the g tensor from its vacuum value.
EPR spectrum can be modeled using the following effective Hamiltonian, bilinear in the total electron
spin S, and the applied uniform magnetic field or nuclear spins, B and II, respectively:
where:
atomic units are used

α is the fine structure constant

the summation I runs over the nuclei
The tensors AI are the hyperfine parameters, and the tensor g is the EPR g-tensor.
Requesting optical properties (DFT)
CASTEP currently implements two approaches for optical properties calculations; one is based on
standard DFT Kohn-Sham orbitals and the other uses more accurate but much more time-consuming
time-dependent DFT (TD-DFT) theory. In this section we consider only DFT Optical properties. Setting up
TD-DFT optical properties calculations are described in the section Requesting electronic excitations (TD-
DFT).
Calculating optical properties produces electronic energies on the Monkhorst-Pack mesh of k-points and
the matrix elements for electronic interband transitions. The CASTEP Analysis dialog can be used to
generate observable optical properties based on this information. Detailed analysis of the impact of
calculation parameters (k-point set, number of empty bands, and so on) on the accuracy of the optical
properties generated can be found in the Optical properties theory topic.
Note: You are not required to use the same exchange-correlation functional in the optical properties
functional to study the optical properties after performing, for example, geometry optimization with
To calculate optical properties
3. Check the Optical properties option on the properties list.
band.
Note: The number of empty bands used should be greater when calculating optical properties
than for band structure or density of states calculations (see the Optical properties theory topic
for more details).
5. Optionally, adjust the density of Monkhorst-Pack k-points used for the optical properties
calculation by using k-point set dropdown list.
6. Click the More... button to open the CASTEP Optical Properties Options dialog. This dialog gives you
complete control over setting up the grid.
7. Check Use separate XC functional for optics calculation on the CASTEP Optical Properties Options
dialog if you want to use, for example, a nonlocal functional for the optical properties calculation.
8. Select the alternative Functional you wish to use from the dropdown list on the same dialog.
Requesting orbital analysis
Although wavefunctions are generated by every CASTEP run, they are not returned to the client by
default, as the file containing the wavefunctions is very large. To perform orbital analysis it is necessary
to explicitly request that these files be returned to the client.
Note: Orbitals are required to calculate the STM profile.

To perform an orbitals analysis

3. Check the Orbitals option on the properties list.
Requesting vibrational properties
CASTEP allows you to set up calculations that provide vibrational frequencies and eigenvectors at a
selected set of q-vectors in the Brillouin zone. Two approaches to calculating these data are provided:
Linear response formalism
Finite displacement method
There are two predefined modes of calculation: the phonon dispersion spectrum along high symmetry
directions and the phonon density of states spectrum, which is a prerequisite for the calculation of
thermodynamic properties.
Note: Phonon calculations take into account existing fixed atom constraints, regardless of the overall
Task setting. Such fixed atoms are excluded from the calculation of vibrational properties, which
corresponds to the "partial Hessian" approach. Constrained lattice dynamics approach is applied for
both linear response and finite displacement approach.
Tip: You must check the Fix fractional position checkbox on the Atom tab of the Edit Constraints
Phonon frequencies from linear response calculations

The linear response scheme treats atomic displacements as perturbations. In addition, an electric field
response is evaluated to calculate a non-analytical correction to longitudinal optical (LO) phonon
frequencies at the Γ-point. Longitudinal and transverse modes at the Γ-point are identical (no LO-TO
splitting), unless this correction is applied.
The linear response scheme allows the calculation of phonon spectra in any commensurate or
incommensurate q-vector of the reciprocal space, thus providing full flexibility in the choice of q-vectors
to be used for calculations. Nevertheless, linear response calculations at a general q-vector are very time
consuming and are often not necessary as a real space dynamical matrix that defines vibrational
properties is often a short range property. This real space dynamical matrix can be calculated using a
coarse Monkhorst-Pack mesh and then used to obtain the phonon spectrum at any given q-vector in
the Brillouin zone. Thus, there two major modes of linear response calculations: direct and using
interpolation.
Limitations of the linear response implementation in CASTEP
The current version of CASTEP has a number of limitations related to phonon calculations. The only
settings that are supported for linear response calculations or for finite displacement calculations that
require LO-TO splitting correction are:
Norm-conserving pseudopotentials (see the Setting up pseudopotentials topic)
Non-spin-polarized calculations (see the Setting system parameters topic)
If any of these restrictions is violated by the current settings, an error message is displayed with an
explanation of the problem. The offending setting must be changed in order to proceed with the
phonon calculation.

Note: Gradient-corrected exchange-correlation functionals are supported in linear response

calculations, although the results may be less accurate than those obtained with LDA and the
computational cost is noticeably higher.
Phonon frequencies from finite displacements calculations

CASTEP provides an alternative method of calculating phonon frequencies that is based on the finite
displacements method (Montanari and Harrison, 2002). This technique is based on numerical
differentiation of forces on atoms that are calculated for a number of unit cells with atomic
displacements. CASTEP determines the optimum number of such displacements automatically, based
on the crystal symmetry. Displacements with a very small magnitude give results that are similar to the
linear response frequencies. An advantage of the finite displacements method is that it is also possible
to investigate phonon anharmonicity by increasing the amplitude of the displacements. A further
important advantage is that none of the linear response limitations mentioned above are relevant for
finite displacements calculations. This method can be used to obtain vibrational frequencies for:
Metallic systems
Spin-polarized systems
Any system treated with efficient ultrasoft potentials
The formalism is based on evaluation of the dynamical matrix at a (coarse) commensurate grid of q-
points at the cost of creating a supercell, and then dynamical matrix is re-interpolated onto a requested
set of q-points. There are two available approaches to dynamical matrix calculation:
Create a large supercell with the size defined by a real space cutoff parameter; the supercell size then
dictates a coarse grid.
Create a set of non-diagonal supercells (Lloyd-Williams and Monserrat, 2015) which are
commensurate with a q-point set of a coarse grid; in this case the coarse grid is defined by the grid
spacing for interpolation.
Limitations of the finite displacements implementation in CASTEP
There is a limitation with the current implementation of the finite displacements method in CASTEP
related to the treatment of the non-analytical term that is responsible for the LO-TO splitting in
insulators. This term is currently calculated using linear response with an electric field as a perturbation;
thus, all the computational restrictions mentioned in the previous section apply to finite displacements
calculations if the LO-TO splitting is requested.
Note: A LO-TO calculation imposes all the restrictions that apply when the linear response technique
is used. You might want to proceed with finite displacement calculations without LO-TO splitting if
these restrictions affect your study. In this case, only TO modes will be reliably produced when there
is LO-TO degeneracy in the results.
Requesting phonon dispersion

Calculating the phonon dispersion produces phonon frequencies and eigenvectors along high symmetry
directions in the Brillouin zone. The standard path for each lattice type is taken from Bradley and
Cracknell (1972). The path can be modified using the Brillouin Zone Path dialog. The density of points
along the path, which affects the appearance of the resulting chart, is controlled by the Quality setting in
the Dispersion section on the CASTEP Phonon Properties Setup dialog.
To calculate phonon dispersion
dialog.


3. Check the Phonons checkbox in the list of properties, then select the Dispersion radio button which
appears below the list.
4. If required, check the Calculate LO-TO splitting checkbox.
5. Select the technique to be used to calculate the phonon frequencies from the Method dropdown
list.
6. Click the More... button to display the CASTEP Phonon Properties Options dialog.
7. For linear response calculations, specify the convergence criterion for the force constants in the
Convergence tolerance text box. If you do not want to carry out a direct calculation, check the Use
interpolation checkbox and specify the q-point separation in the q-vector grid spacing for
interpolation text box.
For finite displacement calculations, specify the cutoff radius to be used to construct the
appropriate supercell in the Supercell defined by cutoff radius text box.
8. Optionally, adjust the density of q-vectors along the high symmetry directions used for the phonon
dispersion calculation using the Quality control in the Dispersion section.
9. If you wish to inspect or modify the Brillouin zone path used for the phonon dispersion calculation,
click the Path... button to display the Brillouin Zone Path dialog and alter the path segments
accordingly.
10. Optionally, accelerate the calculation by using partial Hessian approach - apply fixed atom
constraints to the atoms that are not essential to the calculation (for example substrate atoms in a
molecule on surface calculations).
Requesting phonon density of states
Calculating the phonon density of states produces phonon frequencies and eigenvectors on the regular
Monkhorst-Pack mesh of q-vectors. This information is required to produce either the total or projected
(partial) phonon density of states and, thus, to calculate thermodynamic properties. The quality of the
q-vector set is controlled by the Quality setting in the Density of states section on the CASTEP Phonon
Properties Options dialog.
Note: When you request phonon density of states CASTEP will also calculate atomic displacement
parameters, allowing assignment of temperature factors during analysis.

To calculate the density of states

dialog.
3. Check the Phonons checkbox in the list of properties, then select the Density of states radio button
which appears below the list.
4. If required, check the Calculate LO-TO splitting checkbox.
5. Select the technique to be used to calculate the phonon frequencies from the Method dropdown
list.
6. Click the More... button to display the CASTEP Phonon Properties Options dialog.
7. For linear response calculations, specify the convergence criterion for the electronic eigenvalues in
the Convergence tolerance text box. If you do not want to carry out a direct calculation, check the
Use interpolation checkbox and specify the q-point separation in the q-vector grid spacing for
interpolation text box.
For finite displacement calculations, specify the cutoff radius to be used to construct the
appropriate supercell in the Supercell defined by cutoff radius text box.
8. Optionally, adjust the density of Monkhorst-Pack q-vectors used for the phonon density of states
calculation using the Quality control in the Density of states section.
9. If you wish to inspect or modify the setup of the Monkhorst-Pack grid, click the More... button to
display the Phonon Density of States Options dialog and alter the settings accordingly.
10. Optionally, accelerate the calculation by using partial Hessian approach - apply fixed atom
constraints to the atoms that are not essential to the calculation (for example, substrate atoms in a
molecule on surface calculations).
Tip: If you choose quality gamma frequencies then eigenvectors will be only calculated at the Γ-point,
which determines most of the experimental data on IR or Raman spectra. This can accelerate finite
displacement calculations tremendously as no supercell is constructed for this case. However, the
accuracy of thermodynamic properties obtained with this single q-vector is very poor as no acoustic
degrees of freedom can be taken into account.
Calculating vibrational frequencies of an isolated molecule

CASTEP can be used to calculate vibrational frequencies of isolated molecules as well as the phonon
dispersion of solids. It is recommended that only the Γ-point is used for electronic calculations and that
the Γ-point is requested when performing either phonon dispersion or phonon density of states
calculations. In addition, the all bands/EDFT electronic minimizer is known to be more efficient for
studies of isolated molecules in supercell geometry than the density mixing minimizer. Therefore, it is
recommended that you change the Electronic minimizer setting to All Bands/EDFT on the SCF tab of the
CASTEP Electronic Options dialog when performing such calculations.
Note: Do not calculate LO-TO splitting for a "molecule in a box" system. There is no physical meaning
to this term when studying molecular, rather than crystalline, vibrations.

Guidelines for the successful calculation of vibrational properties using CASTEP

1. Parameters for geometry optimization
The results of a phonon calculation will be inaccurate unless the geometry of the input structure is
well converged. Geometry optimization to a true ground state requires that the forces are well
converged.
In general, using a Quality setting of Ultra-fine for the geometry optimization on the Setup tab of
the CASTEP Calculation dialog should be sufficient for the purposes of obtaining accurate forces, but
the safest procedure is to investigate the convergence of the forces as a function of calculation
parameters - primarily the k-point sampling. It is recommended that you carry out a series of single-
point energy calculations using increasingly dense k-point meshes. Monitor the convergence of the
forces until they converge to within the force tolerance criterion.
2. Geometry optimization of the input structure
Once you have generated reasonably well-converged forces, you can carry out the geometry
optimization. Use the same force convergence tolerance as for the force convergence test. A well-
converged geometry optimization is of little value if the forces are inaccurate because of
convergence errors.
You may wish to perform a fixed-cell or variable-cell geometry optimization, depending on your
goals for the calculation. The lattice-dynamical problem is well defined in either case, but, of course,
the pressure or stress will be different. You should also monitor the convergence of the stress
before carrying out a variable-cell optimization (though the behavior is usually similar to the
convergence of forces).
3. Use of consistent electronic settings
To be a valid lattice dynamics calculation, the phonon run must use the same specification as the
geometry optimization. If you want to change anything of significance, such as the cutoff, XC
functional or k-point sampling, you must carry out a fresh geometry optimization using these new
settings before starting the lattice dynamics run.
4. Checking the convergence of the results
Unfortunately, following the above guidelines does not guarantee that your final phonon
frequencies will be converged to any given tolerance. The only way to determine that this is the case
is to actually check the convergence behavior of the final properties. This requires a subtle
judgment of whether you are measuring a 'primary' change due to the convergence of force
constants or a 'secondary' one consequent on the slightly different geometry.
As noted in the literature, and from experience, phonon frequencies are more sensitive to k-point
convergence than geometries, assuming tolerance criteria of a few cm-1 and a few hundredths of an
angstrom. Acoustic phonons near the Γ-point are the most sensitive, as they depend on near-
cancellation between large force constant terms in the dynamical matrix. Dielectric properties and
Born charges tend to be more sensitive than phonons, on a fractional proportion tolerance.
The ultimate convergence test would require geometry optimization performed for a denser k-point
grid, followed by a new phonon calculation - this is the only way to determine whether the k-point
sampling has an effect on the accuracy of the calculated vibrational frequencies.

Note: Phonon spectra in metallic compounds are very sensitive to the details of the Fermi surface. To
obtain reasonable spectra using linear response method for metals, the k-point sampling must be
extremely dense: much denser than the Fine mesh. It is recommended to consider setting the
Separation parameter on the k-points tab of the CASTEP Electronic Options dialog to less than 0.02. A
clear sign of insufficient quality of k-point sampling is the presence of imaginary acoustic modes near
the Γ-point.
Requesting polarizability, IR, and Raman spectra

Within the electric field linear response formalism, CASTEP enables you to calculate optical (ω = ∞) and
dc (ω = 0) dielectric permittivity or optical (ω = ∞) and static (ω = 0) molecular polarizability. These
properties are calculated when the TASK keyword in the input parameters (.param) file is set to either
Efield or Phonon+Efield. In the latter case, infrared intensities (response to an electric field in the infrared
range) are calculated as well if there is a Γ-point among the phonon k-points.
The calculated results are somewhat sensitive to the value of the scissors correction. This correction
amounts to the difference between the calculated and experimental band gap. It is possible to estimate
this correction when the experimental data are available by performing the band structure run with
CASTEP and comparing the calculated band gap with the experimental value.
To calculate polarizability, IR and Raman spectra
dialog.
3. Check the Polarizability, IR and Raman spectra checkbox in the list of properties.
4. Choose the correct description of the system from the System type dropdown list (Crystal,
Molecule, or Linear molecule). The last two options refer to the supercell description of isolated
molecules.
5. Specify whether to Calculate Raman intensities using the checkbox.
6. Click the More... button to open the CASTEP IR and Raman Options dialog.
7. Optionally, alter the accuracy of the calculation by entering a new value in the Convergence
tolerance field.
8. If the value of the scissors operator is known, enter it in the Scissors operator text box and close the
dialog.
Calculating the polarizability, IR and Raman spectra of an isolated molecule
CASTEP can be used to calculate the electric field response of isolated molecules as well as of solids. It is
recommended that only the Γ-point is used for electronic calculations on molecular systems. In addition,
the all Bands/EDFT electronic minimizer is known to be more efficient for studies of isolated molecules in
supercell geometry than the density mixing minimizer. Therefore, it is recommended that you change
the Electronic minimizer setting to All Bands/EDFT on the SCF tab of the CASTEP Electronic Options
dialog when performing such calculations.
Note: It is important to select the correct description of the system from the System type dropdown
list when calculating the electric field response for a molecular system. The wrong system description
can significantly affect the molecular polarizability values obtained.

Limitations of the electric field response implementation in CASTEP

The current version of CASTEP has a number of limitations related to electric field response calculations;
they are essentially the same as those for phonon calculations. The only settings that are supported for
electric field response calculations are the following:
Norm-conserving pseudopotentials (see the Setting up pseudopotentials topic)
Non-spin-polarized calculations (see the Setting system parameters topic)
Fixed orbital occupancies (see the Setting up SCF parameters topic)
Note: It is not sufficient to use fixed orbital occupancies (that is, by checking the Fix occupancy
checkbox on the SCF tab of the CASTEP Electronic Options dialog) if the system under investigation
should be nonmetallic according to DFT results from a non-spin-polarized calculation. Attempting to
study a metallic system using fixed orbital occupancies will result in poor convergence of the electric
field response calculation; the symptoms of which will very large numbers for IR and Raman
intensities and for polarizability in the output file. If this is the case, check whether your system is
metallic by running either density of states or band structure calculations.
If any of these restrictions is violated by the current settings, an error message will be displayed with an
explanation of the problem. The offending setting must be changed in order to proceed with the
calculation.
Note: Gradient-corrected exchange-correlation functionals are supported in linear response
calculations, although the results may be less accurate than those obtained with LDA and the
computational cost is noticeably higher.
Requesting population analysis

Performing population analysis produces Mulliken charges, Mulliken magnetic moments, Mulliken
partial charges for each angular momentum component, Mulliken bond populations (charge and spin),
and Hirshfeld charges. You can use the Distance cutoff for bond populations option on the Properties
tab to limit the amount of output from the bond population analysis. You can also use the Calculate
band populations option to calculate the band contributions to the Mulliken charges, so that the
results can be used to generate a PDOS chart.
If a system has a P1 symmetry orbital-resolved Mulliken populations are returned for each atom,
specifying the amount of charge in, for example, the px, dxy (and so on) orbitals.
Tip: The Population analysis checkbox on the Properties tab of the CASTEP Calculation dialog is
checked by default.
Note: It is not possible to specify the number of atomic orbitals to be used in the population analysis
explicitly in the CASTEP interface. If the spilling parameter reported in the .castep output file is too
large (more than 5%), it may be that the default CASTEP parameters were insufficient for this
calculation. In such circumstances you should edit the .cell file and change the SPECIES_LCAO_
STATES parameters for atomic species, then run the input files again. The SPECIES_LCAO_
STATES parameter for a species should be set such that it results in a complete set of angular
momentum states. For example, to use a single s and single p state SPECIES_LCAO_STATES
must be 2.

To perform population analysis

3. Ensure that the Population analysis option on the properties list is checked.
4. Optionally, modify the Distance cutoff for bond populations field to include more or less atomic
pairs in the calculation.
5. If you wish to generate partial and local densities of states for the valence band, check the Calculate
band populations option.
Requesting stress analysis
Calculating stress involves performing a stress tensor calculation, even when the cell parameters are
fixed. The stress is a useful measure of the accuracy of the structural description: for example, after
performing geometry optimization with a fixed cell, you can get an idea of how accurate the cell
parameters are from the magnitude of the remaining stress. Similarly, when studying an isolated
molecule in a supercell, the value of the stress provides a guide as to the size of the cell required to
remove unphysical interactions between periodic images.
Note: It is important to use finite basis set correction when calculating the stress tensor (see Setting
up the basis set for details). Choosing either Smart or Always as the Apply finite basis set correction
setting on the Basis tab of the CASTEP Electronic Options dialog will achieve this.
To perform a stress analysis
dialog.
3. Check the Stress checkbox in the list of properties.
5. Click the More... button to display the CASTEP Electronic Options dialog.
7. Select either Smart or Always from the Apply finite basis set correction dropdown list.
Manipulating files
CASTEP is a file-based application which means that all input information is provided in various ASCII text
files and the output is delivered in a mixture of text and binary files. This section describes some file
handling issues which may arise, especially when the CASTEP server is run in a standalone mode and not
through a gateway.
Input files
CASTEP allows you to save input files, for subsequent manual editing instead of running the job directly.
To save input files
2. Click the Files... button to open CASTEP Job Files dialog.
3. Click the Save Files button.
Note: The Save Files button is enabled only if a suitable 3D model document is active.

Only one input file, .param, is displayed in the Project Explorer. This file contains the parameters
specified using the CASTEP interface. However, it also contains a few parameters that allow you to access
functionality which is not supported though the interface. The other input files are hidden, since they
are unlikely to be edited manually.
Input files can be run on a server after they have been edited:
To run CASTEP using an existing set of input files
2. Click the Files... button to open CASTEP Job Files dialog.
3. Click the Run Files button.
Note: The Run Files button is enabled only if a suitable .param file is active.
If your server does not support the gateway protocol, you may have to run CASTEP in standalone mode
using the RunCASTEP.sh or RunCASTEP.bat files provided with the installation.
In such circumstances it is necessary to copy all the input files from the Materials Studio Project folder to
the appropriate directory on the server machine. The scripts required for standalone execution are
provided with accompanying RunCASTEP.Readme files that explain, in detail, how to use them.
Alternatively, you can obtain help by typing one of the following:
RunCASTEP.sh -h
RunCASTEP.sh
Note: The Materials Studio Project folder does not contain the pseudopotential files required to run a
job. When transferring input files to the server, you must therefore determine which pseudopotential
files are required by examining the .cell file. Then you must locate those potential files in Materials
Studio installation, typically in a sub-directory called share\Resources\Quantum\Castep and copy the
required files to the same directory on the server as the rest of the input files.
Output files
Only one output file, .castep, is displayed in the Project Explorer. However, there are many more files
created during a CASTEP run. These are hidden by Materials Studio. All of these output files are placed in
the correct Materials Studio Project folder automatically, when the job is run using the Gateway.
However, if CASTEP is run in standalone mode, the output files must be copied manually from the server
to the appropriate Project folder.
Some output files can be quite large. If these files are not likely to be required to restart the job, then it is
recommended that you delete or archive them periodically.
Restarting a CASTEP calculation
It is not possible to restart a completed CASTEP job automatically using the interface. However, there
are circumstances in which you may wish to do this, for example, if you are running a geometry
optimization which does not converge in the given number of steps, or a you wish to continue your
calculation with manually modified runtime parameters. To restart such jobs you should edit .param
file and add the CONTINUATION keyword to the file.
Note: Any additional changes to this file may make it impossible to restart the CASTEP job
successfully.
Tip: It is possible to remove everything from .param and leave only the CONTINUATION line. This
will ensure that all of the settings remain exactly the same as those from the previous run.

Note: In order to restart a job, the output files from the previous run must be present in the Project
folder. This check and the subsequent transfer of the files to the server happens automatically
whenever CASTEP is used to run an existing file set or to calculate additional properties.
Analyzing CASTEP results

CASTEP results can be analyzed when a job has been completed and all of the output files have been
downloaded successfully to the appropriate results folder.
Select the results to be analyzed by opening the structure document in the results folder or the results
(.castep) file from the CASTEP calculation. This allows you to analyze all related CASTEP results.
Note: The structure is updated automatically on successful download of output files from a
completed CASTEP job that was run using a gateway (the structure is not automatically updated if the
CASTEP job was run in standalone mode).
The atoms in the updated structure document have an extra property, ServerAtomName, associated
with them. This shows the atom sequence numbers as used in the CASTEP output files and can be
seen by labeling atoms in the structure with the ServerAtomName property. (This property will be
seen only in structures generated from CASTEP and other similar applications).
All other analysis functions require you to perform certain actions using the CASTEP Analysis dialog.
Note: Only structure updates take place automatically after a CASTEP job is completed and the
results files have been downloaded successfully (this only applies to jobs that are run on a server
through the gateway, not jobs that are run in a standalone mode). All other analysis functions are
performed manually, using the options on the CASTEP Analysis dialog.
Displaying trajectory and chart data

Depending on the type of calculation performed, a CASTEP run may produce a trajectory document and
one or more chart documents. These documents have a special association with each other because
each of the points on the graphs correspond to a frame in the trajectory.
CASTEP produces a trajectory (.xtd) file whenever you run a geometry optimization, molecular
dynamics or elastic constants calculation, or a transition state search. In all cases, a history of the
optimization is returned in a file called <name> Trajectory.xtd, where <name> is the name used
for the job description on the Job Control tab of the CASTEP Calculation dialog.
When you run a geometry optimization, two chart documents are generated:
<name> Energies.xcd: Contains a plot of total energy vs. frame for all steps of the calculation
<name> Convergence.xcd: Contains three (possibly four) plots that describe the degree of
convergence of the optimization as a function of frame:
Change in energy vs. frame
Maximum Cartesian force vs. frame
Maximum Cartesian step size vs. frame
Maximum stress tensor component vs. frame (for cell optimization runs)
Because these values span several orders of magnitude, the data are plotted on a log10 scale.
Similar charts are produced for each structure in an elastic constants calculation.

When you run a transition state search, a single chart containing a graph of energy vs. reaction
coordinate for each step of the calculation, <name> TSSearch.xcd, is generated. This includes an
individual graph for each LST or QST 'uphill' cycle as well as a graph for each conjugate gradient
minimization. The CASTEP Transition State Search task topic contains more details.
When you run a molecular dynamics simulation, either two or three chart documents are generated:
<name> Constant.xcd: Contains a plot of the constant of motion vs. simulation time
<name> Temperature.xcd: Contains a plot of temperature vs. simulation time
<name> Pressure.xcd: Contains a plot of pressure vs. simulation time (only produced by the
NPH or NPT ensemble)
Trajectory files can be animated using the controls on the Animation toolbar.
If you have access to the Forcite module, you may find some of its dynamics, statistical, and structural
analysis features useful for analyzing trajectories. Refer to the Using Forcite Analysis topic for details.
Creating a trajectory and chart
When you run CASTEP using the Materials Studio interface, the creation and display of these trajectories
and charts is automatic. If you selected Automatically view output on the CASTEP Job Control Options
dialog, the graphs will be displayed automatically on completion of the run. If you selected Update
graphs on the CASTEP Job Control Options dialog, these graphs will be displayed and updated with
intermediate results throughout the course of the calculation.
To create charts from output files generated by a standalone calculation
1. Download the files from the compute server to your PC using the procedure described in Running
CASTEP in standalone mode. Be sure to retrieve the .check, .castep, and .geom, .md, or
.ts files.
2. Select Modules | CASTEP | Analysis from the menu bar.
3. Select Energy evolution from the list on the CASTEP Analysis dialog.
4. Make sure that the .castep file is the currently active document.
5. Click the View button.
If you used the Materials Studio interface to set up and launch your job, you can regenerate the chart
documents by following a similar procedure.
To regenerate charts
1. Open either the .xsd or .castep file and make it the currently active document.
2. Select Modules | CASTEP | Analysis from the menu bar.
3. Select Energy evolution from the list on the CASTEP Analysis dialog.
Animating the trajectory
You can use the controls on the Animation toolbar to animate the trajectory, stepping through each of
the frames of the document. If the chart is open during the animation, the point corresponding to the
active frame will be highlighted.
Chart Viewer point selection
Alternatively, you can use Chart Viewer point selection to display the trajectory frames of the points you
select from the chart document.

To display a trajectory frame for a point on a chart document
1. Choose the Selection tool on the Chart Viewer toolbar to enter selection mode.
2. Making sure you have the corresponding trajectory document open, select a data point on the
chart document.
3. The corresponding trajectory frame is displayed.
4. Drag the mouse over other data points on the chart document to display their corresponding
trajectory frames.
5. If CASTEP generated multiple chart documents, the related data points will be highlighted on all of
them.
Tip: To make it easier to see the chart and trajectory documents, close all the other documents and
then maximize the sizes of these two documents by selecting Window | Tile Vertically from the menu
bar.
Visualizing volumetric data

You can visualize the spatial distribution of electronic charge, electron density difference, electron
localization function, and electrostatic potential calculated by CASTEP. In addition, charge densities of
particular orbitals and the approximate STM profile for surfaces in a slab supercell geometry can be
visualized. The relevant data from the CASTEP results files are used to add a field to the model. This field
can be visualized in a variety of ways (direct field visualization, isosurfaces, slices, and so on).
Electronic charge
Electron density difference
Electron localization function
SCF local potential
Orbitals
STM profile
Field visualization
Electronic charge
Materials Studio uses the information stored in the CASTEP binary output file to create a field that
corresponds to the electronic charge. When you analyze a spin-polarized calculation, you can create
additional separate fields for the density of spin-up (alpha) or spin-down (beta) electrons, as well as a
field for the spin density (the difference between the density of alpha and beta electrons). The latter field
allows you to visualize the spatial distribution of the magnetic moment in a spin-polarized system.
Note: Maxima in the electronic density field correspond to interatomic bonds or to the position of
atoms that have semicore states which are explicitly treated as valence. When there are no semicore
states in the system (this can be verified by analyzing the atomic charges displayed on the Potentials
tab of the CASTEP Electronic Options dialog), the density will display minima at the positions of
atomic nuclei. This is to be expected in the pseudopotential formalism.

To create a density field

1. Choose Modules | CASTEP | Analysis from the menu bar to open the CASTEP Analysis dialog.
2. Select Electron density from the list of properties.
3. Ensure that the 3D Atomistic document to be analyzed is the active document.
4. For spin-polarized calculations, select the type of field required from the Density field dropdown list.
5. Optionally, check the View isosurface on import checkbox to automatically create an isosurface
when the density field is imported.
6. Click the Import button.
You also have the option of creating a plain text file which contains the values of charge (and spin, when
appropriate) density on a regular grid along three lattice vectors. The file has the extension .charg_
frm and is hidden by default. Select Tools | Folder Options... in the Windows File Explorer to open the
Folder Options dialog, then select the View tab and click the Show hidden files and folders radio button
to reveal the hidden file. The format of the file is self-explanatory:
a b c Charge
1 1 1 1.8133362740
2 1 1 1.5071161497
3 1 1 1.1111633102
4 1 1 0.9584556846
or, for a spin-polarized calculation:

a b c Charge Spin
1 1 1 1.8130116660 0.0006370238
2 1 1 1.5068114569 0.0004814296
3 1 1 1.1108593919 0.0002249406
4 1 1 0.9580778273 0.0001768619
Note: The charge and spin density in the .charg_frm file are in the same units as those used by
CASTEP during calculations. The values are normalized to the number of electrons per cell. The
density fields displayed in the 3D model are, however, normalized to the number of electrons per Å3.
To create a plain text density file
2. Select Electron density from the list of properties.
3. Click the Save density to file button.
Materials Studio provides the option of generating the electron density difference in two different ways:
Electron density difference with respect to a linear combination of the atomic densities
Electron density difference with respect to a linear combination of the densities of sets of atoms
contained in the model
The former option produces a density difference field which shows the changes in the electron
distribution that are due to formation of all the bonds in the system. This object is appropriate for bulk
solids to illustrate the charge redistribution due to chemical bonding.
The latter option generates a density difference field which effectively corresponds only to the formation
of bonds between atoms in different sets and to charge redistribution within the sets that is due to the
presence of other sets. This property is useful to describe such processes as bonding of molecule(s) to
external and internal (for example, zeolites) surfaces or creation of large molecules from smaller
fragments.

To create a density difference field

2. Select Electron density difference from the list of properties.
4. Use the Use atomic densities checkbox to request the density difference with respect to a linear
combination of the atomic densities. The density difference with respect to the sets of atoms will be
produced when this checkbox is unchecked.
when the potential field is imported.
7. A field is created in the model; its name is either "CASTEP density difference from atoms" or
"CASTEP density difference from sets", depending on whether the Use atomic densities checkbox is
checked.
Note: Analysis based on atomic densities requires the presence of a binary file with the extension
.chdiff; analysis based on sets of atoms requires that for each set of input files, seed_
Subset*.*, there are binary files with the extension .check present. The Import button is
disabled if the files required for the current setting of the Use atomic densities checkbox are not
present in the results folder.

Materials Studio uses the information stored in the CASTEP binary output file to create a field that
corresponds to the localization of electrons.
To create an electron localization function field
2. Select Electron localization function from the list of properties.
when the density field is imported.
6. A field is created in the model, named "CASTEP electron localization function".
SCF local potential
Materials Studio uses the information stored in the binary .cst_esp file to create a field that
corresponds to the local part of the Kohn-Sham potential. In fact, the data in the file correspond to
minus a Kohn-Sham potential. Thus, this field is closely related to the electrostatic potential used in
quantum chemistry programs, where it represents the electrostatic energy of a proton at a given point.
The units of the potential are eV/electron.
The local SCF potential analyzed in Materials Studio includes all the DFT contributions, except for the
nonlocal part of the pseudopotential: the Hartree term, the local pseudopotential term, and the
exchange-correlation term. This potential can be used to analyze important solid-state properties such
as band offsets and work function (the latter is a specific case of the band offset calculation where one of
the materials is a vacuum). An excellent description of the formalism for band offset calculations based
on CASTEP results is given by Al Allak and Clark (2001).

To create a local potential field

2. Select Potentials from the list of properties.
4. Select the type of field required from the Potential field dropdown list.
Note: Materials Studio currently supports only the local SCF potential field type.
Orbitals
Materials Studio uses the information stored by CASTEP in a binary .check file to create a field that
corresponds to any of the orbitals in the system. In this context, the orbital is the square of the absolute
value of the wavefunction for a given electronic band, summed over all k-points. A band is defined by
the position of its eigenvalue in the ordered list of electronic energies at each k-point. For example,
orbital (or band) number 3 is obtained by summation over all k-points of the wavefunctions with the
third lowest energy. The sum of the "orbital densities" obtained in this way gives the total electron
density of the crystal.
Note: Because of the size of the .check file orbital analysis is only available if orbitals are explicitly
requested.
The Filter dropdown list, which becomes available on the CASTEP Analysis dialog when Orbitals is
selected from the list of properties, allows you to control which orbitals are displayed in the table:
Alpha displays data for alpha-spin orbitals (spin up) only
Beta displays data for beta-spin orbitals (spin down) only
Note: For non-spin-polarized calculations, this option is not available.
The orbital analysis table provides you with a list of eigenvalues and information about each orbital. The
list of eigenvalues starts with the lowest energy orbital. The accompanying information includes:
N - number of the orbital, with 1 corresponding to the lowest energy orbital.
s - spin: + for alpha, - for beta.
Note: In a non-spin-polarized calculation, all orbitals are labeled +.
From - lowest value of the energy of the Nth band at any k-point (in eV)
To - highest value of the energy of the Nth band at any k-point (in eV)
You can artificially change the band gap value for insulators or semiconductors by using the scissors
operator. This parameter effectively describes the difference between the theoretical and experimental
band gap values. When the experimental value is known, you can perform a band structure calculation
to find the theoretical band gap. Then, simply set the scissors operator to the difference between the
two values. The eigenvalues of the conduction band states displayed in the scrollable list will be shifted
upward by the value of the scissors operator.

To create an orbital field

2. Select Orbitals from the list of properties.
4. From the scrollable list, select the row(s) corresponding to the orbital(s) you wish to display.
Tip: Multiple selections are allowed. To select more than one orbital, hold down the SHIFT key
and click on the first and last orbitals in the block you want to select, or hold down the CTRL key
and click to select orbitals individually.
Note: The units for the isovalues are e/Å3 and correspond to the wavefunction density, ψ2.
STM profile
CASTEP models the scanning transmission microscope (STM) profile by representing it as an isosurface
of the electron density generated only by states at a certain energy away from the Fermi level. The
distance from the Fermi level corresponds to the applied bias in actual STM experiments. Positive bias
corresponds to the imaging of empty (conduction) states, while negative bias produces images of
occupied (valence) states. This approach neglects the actual geometry of the STM tip and makes use of
the Tersoff-Hamman approximation for tunneling transport (Tersoff and Hamman, 1985).
STM profile visualization makes sense only for models that represent surfaces in the slab supercell
geometry. In addition, information about charge density at a distance from the surface is likely to be
inaccurate as a result of the DFT failing to reproduce the asymptotics of the wavefunction decay into a
vacuum.
Note: Because of the size of the .check file STM analysis is available only if orbitals are explicitly
requested.
Note: Visualization of the images created by conduction band states requires that the calculation was
performed with an increased number of empty bands. The recommended procedure is to use
electronic density of states (DOS) calculations and specify a sufficiently high number of empty states.
To create an STM profile
2. Select STM profile from the list of properties.
4. Specify the STM bias value.
6. Use field visualization tools to create an isosurface that represents the STM profile.
Field visualization
Materials Studio provides a number of tools for field visualization. They are accessed from the Volume
Visualization toolbar and Field, Isosurface, and Slice tabs on the Display Style dialog.

The Volume Visualization toolbar provides access to the Volumetric Selection dialog, which enables you
to specify the field to be visualized and set visibility attributes for fields, slices, and isosurfaces. This
toolbar also contains controls for creating new isosurfaces and slices, including the shortcuts for
orienting the slice based on either the cell axes or the coordinates of selected atoms. The Color Maps
dialog, which can also be accessed from the Volume Visualization toolbar, provides control over the
coloring of volumetric objects (it also provides useful shortcuts for determining the minimum and
maximum values of the field).
The Field tab of the Display Style dialog allows you to visualize the field directly using either the Dots or
Volume display styles.
The Isosurface tab of the Display Style dialog allows you to alter the visualization style of a selected
isosurface, change its isovalue, or use another field for color mapping.
The Slice tab of the Display Style dialog allows you to alter the visualization style of a selected slice.
Note: The volumetric visualization tabs on the Display Style dialog are displayed only if an object of
the relevant type is present in the active document. If a field, isosurface, or slice is selected, for
example by using the Volumetric Selection dialog, the volumetric visualization tabs that are not
relevant to the selection will be removed from the Display Style dialog.
Tip: Field visualization in Materials Studio fully supports periodic display. You can use the Field tab on
the Display Style dialog to change the range of a field to display more or less than one unit cell of a
structure.
Note: The default settings for field visualization result in the fields being displayed over one unit cell of
a structure. Use the In-Cell display mode for the lattice (accessible from the Lattice tab of the Display
Style dialog) to make sure that the field is positioned around the displayed atoms.
Displaying band structure charts

Band structure charts show how electronic energies depend on k-vector, along high symmetry
directions in the Brillouin zone. These charts provide a useful tool for qualitative analysis of the
electronic structure of a material, for example, it is easy to identify the narrow bands of d and f states as
opposed to the free electron like bands that correspond to s and p electrons. It is also instructive to look
for directions with relatively flat, dispersionless bands, as these directions are likely to contribute
strongly to optical absorption. Thus, allowing explanation of the anisotropy of optical properties. The
energy band gap is also easily deduced from the band structure plots as it normally corresponds to the
energy difference between two states at high symmetry points.
An example of the CASTEP output for band structure is shown in Figure 1. Electronic states with different
spins are presented using different colors and the Fermi level is shown with the dashed line. All energies
are relative to the Fermi level (or to the top of the valence band in the case of insulators or
semiconductors). The labels along the X axis of the band structure graph correspond to the standard
definitions of high symmetry points for the given lattice type (Bradley and Cracknell, 1972). The Γ-point is
denoted by a G.
The density of states included in this plot was created using Interpolation as an Integration method and
Alpha and Beta as the DOS display.
Note: If you have calculated DOS for a spin polarized system with a non-zero initial spin and the total
spin is not optimized two charts will automatically be displayed, <seedname> Band
Structure Alpha.xcd and <seedname> Band Structure Beta.xcd.

Figure 1. Band structure with DOS for Fe (spin-polarized GGA calculation).

To create a band structure chart
1. Choose Modules | CASTEP | Analysis from the Materials Studio menu bar.
2. Select Band structure from the list of properties.
3. Use Results file selector to pick the appropriate results file (it should have a BandStr suffix).
4. Select a required display style (Points or Lines) from the Graph style dropdown list.
5. Optionally, check Show DOS and set the relevant DOS options.
7. A new chart document, seedname Band Structure.xcd, is created in the results folder.
Displaying core level spectra

The CASTEP Analysis dialog can be used to generate observable core level spectra based on electronic
energies on the Monkhorst-Pack mesh of k-points obtained during a calculation. Detailed analysis of the
impact of calculation parameters (k-point set, number of empty bands, and so on) on the accuracy of
the spectra generated can be found in the core level spectroscopy theory topic.
Note: Core level spectra can only be calculated for single atoms. One atom should be selected in the
active 3D Atomistic document before carrying out a core level spectroscopy analysis.

To create a core level spectrum

2. Select Core level spectroscopy from the list of properties.
3. In the 3D Atomistic document containing the 3D periodic structure, select the atom for which you
wish to simulate a core level spectrum. Click the Atom Selection button on the CASTEP Analysis
dialog to open the Atom Selection dialog.
4. Use the Results file selector to pick the results file or make the seedname_EELS.castep file the
active document.
5. Select the electron configuration of the Spectrum.
6. Specify the Type of spectrum you want to calculate, options are Absorption and Emission.
7. Click the More... button to open the CASTEP EELS Analysis Options dialog.
8. Set the Instrumental smearing value.
9. Specify whether to take Lifetime effects into account by checking or unchecking the checkbox, if
checked set the Core level broadening value.
10. Specify whether to take Include spin-orbit splitting into account by checking or unchecking the
checkbox, if checked set the Spin-orbit splitting value and close the CASTEP EELS Analysis Options
dialog.
11. Select the incident radiation polarization from the Calculation dropdown list. If you specify
Polarized radiation choose the direction of the Polarization of the incident radiation in fractional
(lattice) coordinates.
12. Make the 3D periodic structure the active document and click the View button.
13. A new chart document, seedname EELS.xcd, is created in the results folder and becomes the
active document.
Note: If you carry out several core level spectroscopy analyses, each new spectrum will be displayed
in a new chart document.
Displaying density of states charts

Density of states (DOS) and partial density of states (PDOS) charts give a quick qualitative picture of the
electronic structure of a material and sometimes they can be related directly to experimental
spectroscopic results.
Note: If you have calculated DOS for a spin polarized system and the total spin is not optimized two
charts will automatically be displayed, <seedname> DOS Alpha.xcd and <seedname> DOS
Beta.xcd.
Full density of states

Materials Studio can produce DOS plots from any .bands CASTEP output file. These files are hidden in
the Project Explorer but a .bands file is generated with every .castep file. All the files that can be
used in the analysis of the current calculation will be presented in the results file selector. However, it is
recommended that you create DOS plots based on the results of a band structure calculation that only
uses k-points in high-symmetry directions.
Tip: When evaluating DOS, use only the results of eigenvalues calculations on the Monkhorst-Pack
grid. If you have more than one such set of results, for example, DOS and Optics, select the one with
the highest density of k-points, that is, the highest Monkhorst-Pack mesh parameters.

To create a DOS chart

2. Select Density of states from the list of properties.
3. Use Results file selector to pick the right results file.
4. Select Full to display the total DOS.
5. For spin-polarized calculations, select the required DOS component from the DOS display
dropdown list.
6. Specify the Function to use, either DOS or Integrated DOS.
7. Optionally, click the More... button to open the CASTEP DOS Analysis Options dialog. Set the
Integration method and other options, Interpolation gives more accurate results than the
Smearing method, although it is slightly slower.
9. A new chart document, seedname DOS.xcd, is created in the results folder.
Partial density of states
Materials Studio produces PDOS plots for certain angular momenta on selected atoms. The Sum curve
represents the local density of states (LDOS) when one atom is selected. If more than one atom is
selected, the contributions in each angular momentum channel from all selected atoms are added
together. When no atoms are selected the behavior is the same as if all atoms were selected.
Note: PDOS analysis formalism is not valid for high energy states in the conduction band: PDOS
representation will usually decay to zero at about 20 eV above the Fermi level. This is related to the
fact that expansion of essentially free electron states in terms of a limited number of atomic-like basis
functions is impossible to carry out with any degree of accuracy. Only the valence band and lower
part of the conduction band are meaningful in the PDOS plot.
Figure 1. PDOS for BN. The left window is for boron, the right for nitrogen.

To create a PDOS chart

2. Select Density of states from the list of properties.
4. Select Partial to display the partial DOS.
5. Check the required angular momentum components for the PDOS.
6. Select the atom or atoms in the model, for which the PDOS is to be created.
7. For spin-polarized calculations, select the required DOS component from the DOS display
dropdown list.
8. Optionally, set additional CASTEP DOS analysis options. The Interpolation Integration method gives
more accurate results than the Smearing method, although it is slightly slower.
10. A new chart document, seedname PDOS.xcd, is created in the results folder.
Tip: You should rename this file to indicate the atoms on which it is based. In the example above (see
Figure 1) suitable names for the two files created might be BN N PDOS.xcd and BN B
PDOS.xcd (the default names are BN PDOS.xcd and BN PDOS (2).xcd).
Calculating elastic constants

CASTEP results for the Elastic Constants task are returned as a set of .castep output files. Each of
them represents a geometry optimization run with a fixed cell, for a given strain pattern and strain
amplitude. The naming convention for these files is:
seedname_cij__m__n
Where m is the current strain pattern and n is the current strain amplitude for the given pattern.
CASTEP can then be used to analyze the calculated stress tensors for each of these runs and generate a
file with information about elastic properties. The information in this file includes a summary of the
input strains and calculated stresses; results of linear fitting for each strain pattern, including quality of
the fit; the correspondence between calculated stresses and elastic constants for a given symmetry; a
table of elastic constants, Cij, and elastic compliances, Sij; and finally, the derived properties such as bulk
modulus and its inverse, compressibility, Young modulus and Poisson ratios for three directions and the
Lamé constants that are needed for modeling the material as an isotropic medium.
To calculate elastic constants
2. Select Elastic constants from the list of properties.
3. Use the Results file selector to pick the appropriate results file.
4. Click the Calculate button.
5. A new text document, seedname Elastic Constants.txt, is created in the results folder.
Description of the elastic constants file
Below, the example of a hexagonal crystal, Cd, is used to explain the contents of the Elastic
Constants.txt output file produced by CASTEP.
Two strain patterns are required for this lattice type. For each strain pattern there is a summary of
calculated stresses as extracted from the respective .castep files:

Summary of the calculated stresses

**********************************
Strain pattern: 1
======================
Current amplitude: 1
Transformed stress tensor (GPa) :
0.103397 -0.000000 -0.000000
-0.000000 0.103397 -0.000000
-0.000000 -0.000000 0.141636
Current amplitude: 2
Transformed stress tensor (GPa) :
0.012212 -0.000000 -0.000000
-0.000000 0.012212 -0.000000
-0.000000 -0.000000 0.027695
....
Information about the connection between components of the stress, strain, and elastic constants
tensors is provided. At this stage each elastic constant is represented by a single compact index rather
than by a pair of ij indices. The correspondence between the compact notation and the conventional
indexing is provided later in the file:
Stress corresponds to elastic coefficients (compact notation):
8 8 3 0 0 0
as induced by the strain components:

3 3 3 0 0 0
A linear fit of the stress-strain relationship for each component of the stress is given in the following
format:
Stress Cij value of value of
index index stress strain
1 8 0.103397 -0.003000
1 8 0.012212 -0.001000
1 8 -0.076634 0.001000
1 8 -0.163088 0.003000
C (gradient) : 44.415050
Error on C : 0.374023
Correlation coeff: 0.999929
Stress intercept : -0.031028
The gradient provides the value of the elastic constant (or a linear combination of elastic constants), the
quality of the fit, indicated by the correlation coefficient, provides the statistical uncertainty of that
value. The stress intercept value is not used in further analysis, it is simply an indication of how far the
converged ground state was from the initial structure.
The results for all the strain patterns are then summarized:
============================
Summary of elastic constants
============================
id i j Cij (GPa)
1 1 1 127.56650 +/- 1.588
3 3 3 56.99120 +/- 0.051
4 4 4 25.73690 +/- 0.165
7 1 2 48.06835 +/- 0.329
8 1 3 44.44692 +/- 0.180

The errors are only provided when more than two values for the strain amplitude were used, since there
is no statistical uncertainty associated with fitting a straight line to only two points.
Elastic constants are then presented in a conventional 6×6 tensor form, followed by a similar 6×6
representation of the compliances:
=====================================
Elastic Stiffness Constants Cij (GPa)
=====================================
127.56650 48.06835 44.44692 0.00000 0.00000 0.00000

48.06835 127.56650 44.44692 0.00000 0.00000 0.00000
44.44692 44.44692 56.99120 0.00000 0.00000 0.00000
0.00000 0.00000 0.00000 25.73690 0.00000 0.00000
0.00000 0.00000 0.00000 0.00000 25.73690 0.00000
0.00000 0.00000 0.00000 0.00000 0.00000 39.74908
========================================
Elastic Compliance Constants Sij (1/GPa)
========================================
0.0109928 -0.0015861 -0.0073362 0.0000000 0.0000000 0.0000000

-0.0015861 0.0109928 -0.0073362 0.0000000 0.0000000 0.0000000
-0.0073362 -0.0073362 0.0289894 0.0000000 0.0000000 0.0000000
0.0000000 0.0000000 0.0000000 0.0388547 0.0000000 0.0000000
0.0000000 0.0000000 0.0000000 0.0000000 0.0388547 0.0000000
0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0251578
The final part of the file contains the derived properties:

Bulk modulus = 54.17693 +/- 0.080 (GPa)
Compressibility = 0.01846 (1/GPa)
Elastic Debye temperature = 209.41266 K

Averaged sound velocity = 1939.37187 (m/s)
Axis Young Modulus Poisson Ratios

(GPa)
X 90.96865 Exy= 0.1443 Exz= 0.6674
Y 90.96865 Eyx= 0.1443 Eyz= 0.6674
Z 34.49534 Ezx= 0.2531 Ezy= 0.2531
The elastic Debye temperature is evaluated according to the recipe by Anderson (1963), where the
averaged sound velocity is evaluated numerically as an integral over all propagation directions. The
Debye temperature is proportional to the averaged sound velocity, v m:
Where:
h is the Planck constant
k is the Boltzmann constant
N is Avogadro's number
ρ is the density
M is the molecular weight of the solid
q is the number of atoms in the molecule.

The last section of the file contains average properties that describe the elastic response of a polycrystal,
for example:
====================================================
Elastic constants for polycrystalline material (GPa)
====================================================
Voigt Reuss Hill
Bulk modulus : 65.11651 54.17693 59.64672
Shear modulus (Lame Mu) : 29.92204 25.97242 27.94723
Lame lambda : 45.16848 36.86199 41.01523
Young modulus : 77.84279 67.18163 72.51599
Poisson ratio : 0.30076 0.29332 0.29737
Hardness (Tian 2012) : 4.21526 4.00144 4.10621
Universal anisotropy index: 0.96227
This output contains the bulk modulus, shear modulus, Young modulus, and Poisson ratio averaged
according to Voigt, Reuss, and Hill schemes (Nye 1957).
In addition an universal anisotropy index suggested by Ranganathan and Ostoja-Starzewski (2008) is
evaluated.
Vickers hardness in GPa is evaluated based on the Tian (2012) empirical formula that expresses hardness
in terms of the polycrystalline bulk, B, and shear, G, moduli (using Pugh's modulus ratio, k=G/B):
The correlation between the results from this macroscopic model and experimentally measured
hardness values is quite good when hardness is larger than 5 GPa, but empirical formula overestimates
hardness of softer materials.
Note: The empirical expression for Vickers hardness cannot be applied if the calculated shear
modulus is negative (this can happen, for example, when the calculation settings are not sufficiently
accurate). In such a case the summary report will not include the hardness.
Visualizing Fermi surfaces

Fermi surfaces are generated from information from CASTEP calculations which is stored in the .bands
output file. Fermi surfaces can be considered as the energy isosurfaces in reciprocal space.
Tip: To ensure that the generated Fermi surface(s) are reliable you must use as many k-points as
computational resources will allow when setting up the calculation.
To create a Fermi surface
2. Select Fermi surface from the list of properties.
4. Select the Band for which to display the Fermi surface.

To change the Fermi level used for the Fermi surface

1. Create a Fermi surface according to the steps above.
2. Open the Display Style dialog and select the Isosurface tab.
3. In the Generation section change the Isovalue. The Fermi surface will be updated appropriately.
Visualizing vibrational spectra

When a CASTEP calculation returns a Hessian (dynamical matrix) at the Γ-point, then vibrational
frequencies for the bonds in the system being studied can be calculated and visualized using the
Vibrational Analysis tool.
Note: After a CASTEP job that included calculation of the electric field response (that is, the
Polarizability, IR and Raman spectra checkbox was checked on the Properties tab of the CASTEP
Calculation dialog) is complete and the results files have been downloaded successfully, Materials
Studio will automatically import the Hessian matrix, provided that the CASTEP job was not a
Properties run.
A dynamical matrix is returned if the TASK keyword in the input parameters (.param) file is set to either
Efield or Phonon+Efield and there is a Γ-point among the phonon k-vectors. You can achieve this either
by checking the Polarizability, IR and Raman spectra checkbox on the Properties tab of the CASTEP
Calculation dialog or, alternatively, if you wish to calculate the phonon dispersion or phonon density of
states, by checking the Phonons checkbox in the list on the Properties tab, checking the Dispersion or
Density of states checkboxes, as appropriate, that appear below the list, and ensuring that there is a Γ-
point in the q-vector set.
IR spectra
In order to carry out a vibrational analysis, you will need to import a Hessian matrix from the output of a
CASTEP run.
To import a Hessian and display an IR spectrum
1. Choose Modules | CASTEP | Analysis from the menu bar to display the CASTEP Analysis dialog.
2. Select IR spectrum from the list of options at the top of the dialog.
3. Ensure that the 3D Atomistic document to be updated is the active document.
4. Click the Import Hessian from CASTEP output button.
If you requested that the electric field response be calculated as part of the CASTEP job by checking the
Polarizability, IR and Raman spectra checkbox on the Properties tab of the CASTEP Calculation dialog,
you will be able to display vibrational mode frequencies and absorption intensities for the structure
being studied in the form of a list of values or graphically as a vibrational spectrum using the Vibrational
Analysis tool.

Raman spectra
To display a Raman spectrum
2. Select Raman spectrum from the list of options at the top of the dialog.
4. Ensure that the 3D Atomistic document containing the structure is the active document.
5. Select the Function of the mode to be calculated.
6. If the Function is set to Intensity set the Temperature.
7. Set the Smearing value to be used.
8. Select the Units for the X axis.
9. Specify whether to reverse the wavenumber and intensity axes.
11. A new chart document, seedname Raman.xcd, is created in the results folder.
Displaying NMR results

A CASTEP NMR calculation computes the chemical shielding tensor and the electric field gradients for all
of the atoms in the system.
Note: NMR properties are dynamic (that is, they are not present on atoms until they are assigned
during analysis).
To display the shielding tensor
2. Select NMR from the list of properties.
3. Make sure that the desired 3D Atomistic document is the active document.
4. Click the Assign isotropic chemical shielding to structure button to import the data into the model.
5. Right-click in the 3D Viewer and select Label from the shortcut menu. Set the Object type to Atom,
select NMRShielding from the Properties list, and click the Apply button to display the shielding
tensors.
To display the electric field gradients
3. Make sure that the desired 3D Atomistic document is the active document.
4. Click the Assign electric field gradients to structure button to import the data into the model.
select EFGQuadrupolarCoupling or EFGAsymmetry, as appropriate, from the Properties list, and
click the Apply button to display the electric field gradients.

To display the J-coupling constants

3. Use Results file selector to pick the right results file; in this case it should be a seedname_
NMRJC.castep file.
4. Click the Show J-coupling constants button to generate and open a study table reporting the
calculated J-coupling constants. The study table document will be named seedname_NMRJC
JCoupling.std.
The study table contains two sheets, one with the summary of the results (atom pairs,
corresponding interatomic distances, and isotropic and anisotropic components of the J-coupling
tensor) and one with the detailed breakdown of contributions to the isotropic coupling (Fermi
contact term, spin-dipole term, paramagnetic, and diamagnetic contributions).
select ServerAtomName from the Properties list, and click the Apply button to display the atom
names that are shown in the first two columns of the Summary sheet of the study table.
Displaying optical properties

Analysis of optical properties involves two main steps.
Dielectric function calculation
When a CASTEP calculation returns the matrix elements for electronic interband transitions (Eq. CASTEP
56) in the (hidden) file .cst_ome, it is necessary to calculate the dielectric function using Eq. CASTEP
55. This calculation results in the creation of a grid document that contains two sheets. The first is the
summary of the calculation that includes the value of the scissors operator, the geometry of the
calculation and the smearing applied. The second sheet contains a table of the real and imaginary parts
of the dielectric function versus the photon energy (eV).
It is important to set the parameters for this type of calculation correctly in order to be able to compare
the results obtained with experimental optical constants.
Scissors operator: This parameter effectively describes the difference between the theoretical and
experimental band gap values. When the experimental value is known, you can perform a band
structure calculation to find the theoretical band gap. Then simply set the scissors operator to the
difference between the two values.
Tip: When there is no experimental band gap value but there are data on the dielectric function, you
can repeat the calculations with varying scissors operator values and select the one that gives a
theoretical absorption edge which matches the experimental value.
In the absence of any experimental data, use a fixed proportion of the theoretical band gap as the
scissors operator, for example 25%. This approach allows you to study trends in optical properties
across a family of similar compounds.
Calculation: This parameter and the related Polarization or Incidence settings, specify the experimental
geometry. These are irrelevant for optically isotropic crystals but they are necessary to study anisotropy
of optical properties in crystals with lower symmetry. A good example of the theoretical study of optical
anisotropy of crystalline polymers was given by Ambros-Drachl et al. (1995). A more detailed discussion
of the meaning of these settings is given in the Optical properties theory topic.
Smearing: This parameter specifies the width of the Gaussian broadening that is used to produce the
dielectric function. It is similar to the broadening that is used in density of states calculations.

To create a dielectric function grid

2. Select Optical properties from the list of properties.
4. Select the geometry of the calculation from the Calculation dropdown list.
If Polarized geometry is selected, specify the Polarization direction in the text boxes.
If Unpolarized geometry is selected, specify the Incidence direction in the text boxes.
If Polycrystalline geometry is selected, no additional parameters need to be specified.
5. Specify a Smearing value in the text box (0.5 eV is a good default setting).
7. A new grid document, seedname Optical Properties.xgd, is created in the results
folder and becomes the active document.
Display optical constants
The following optical constants can be evaluated based on the calculated dielectric function:
Reflectivity
Absorption
Refractive index, n and k
Complex optical conductivity
Energy loss function
Any of these constants and the complex dielectric function itself, can be plotted using Materials Studio.
The only additional information that might be required are the Drude correction parameters.
The empirical Drude contribution to the spectra is due to intraband excitations that are not included in
the spectra calculated by CASTEP. The Drude contribution, which may be non-zero only for metals and
semi-metals, is determined by the DC Conductivity and Drude Damping parameters. Appropriate values
for these quantities cover a wide range and are usually taken from experiment. A typical value of the
Drude Damping parameter for metals is 0.05 eV. Typical values for the DC Conductivity in metals are
around 250 eV. But it must be 0 for insulators. Another common unit for the DC conductivity is 1/
(Ohm*cm). The conversion factor between this unit and eV is 1/(Ohm*cm) = 5.924 × 10-4 eV.

To create a chart with optical properties

2. Select Optical properties from the list of properties.
3. Ensure that the grid document, seedname Optical Properties.xgd, is active.
4. Specify the property to be plotted using the Function dropdown list.
Tip: If the system is a molecule in the box the only relevant property to display is the Absorption
calculated for Polycrystalline geometry.
5. Specify the energy units for the plot using Units dropdown list.
6. Set the Drude correction parameters for metallic systems. Click the More... button to access the
Optics Analysis Options dialog.
Tip: Ensure that the Drude term is ignored for the nonmetallic systems, that is, check that the DC
Conductivity is 0 on the CASTEP Optical Properties Options dialog.
8. A new chart document, seedname Optical Properties.xcd, is created in the results folder. The
summary from the first sheet of the grid document is used as the graph title to assist in
identification of the graphs.
Note: The View button is enabled only if a suitable grid document is active.
Tip: If the only experimental information available is the value of the static dielectric constant, it is still
possible to assess the value of the scissors operator. Calculate the refractive index repeatedly, using
different scissors operator values and select the one that gives the best fit between the calculated n(0)
value and the square root of the experimental static dielectric constant.
Displaying phonon dispersion and density of states

Phonon dispersion curves show how phonon energy depends on the q-vector, along high symmetry
directions in the Brillouin zone. This information can be obtained experimentally from neutron
scattering experiments on single crystals. Such experimental data are available for only a small number
of materials and thus, theoretical dispersion curves are useful for both establishing the validity of a
modeling approach and to demonstrate the predictive power of ab initio calculations.
In certain circumstances it is possible to measure the density of states (DOS) rather than the phonon
dispersion. Furthermore, the electron-phonon interaction function, which is directly related to the
phonon DOS can be measured directly in the tunneling experiments (see, for example, Yanson, 1988). It
is therefore important to be able to calculate phonon DOS from first principles, in order to compare the
results with experimentally observed spectra.
Materials Studio can produce phonon dispersion and DOS charts from any .phonon CASTEP output
file. These files are hidden in the Project Explorer but a .phonon file is generated with every .castep
file that has a PhonDisp or PhonDOS suffix. All the files that can be used in the analysis of the current
calculation will be presented in the results file selector. However, it is not recommended that you create
phonon DOS plots based on the results of a phonon dispersion calculation that only uses q-vectors in
high-symmetry directions.
Tip: When evaluating phonon DOS, use only the results of the phonon calculations on the
Monkhorst-Pack grid.

To create a phonon dispersion chart

2. Select Phonon dispersion from the list of properties.
3. Use Results file selector to pick the appropriate results file (it should have a PhonDisp suffix).
4. Select the required frequency units for the chart from the Units dropdown list.
5. Select a required display style (Points or Line) from the Graph style dropdown list.
6. Optionally, check Show DOS and set the relevant DOS options.
8. A new chart document, seedname Phonon Dispersion.xcd, is created in the results
folder.
To create a phonon DOS chart
2. Select Phonon density of states from the list of properties.
3. Use Results file selector to pick the right results file (it should have a PhonDOS suffix).
4. Select a required DOS type (Full or Partial) from the DOS display dropdown list.
5. Optionally, set additional CASTEP Phonon DOS analysis options. The Interpolation Integration
method gives more accurate results than the Smearing method, although it is slightly slower.
7. A new chart document, seedname DOS.xcd, is created in the results folder when Full density of
states is selected. A document seedname PDOS.xcd, is created in the results folder when Partial
density of states is selected.
Displaying population analysis results

A CASTEP calculation can compute atomic charges, spins, and bond orders using Mulliken analysis, and
atomic charges using Hirshfeld analysis.
Note: CASTEP bond orders may be incorrect for small unit cells, when an atom is bonded to a number
of periodic images of itself. For example, bond orders for the primitive cell of silicon are reported as
3.0, while the same calculation for the conventional cell gives 0.75. The factor of four appears because
CASTEP sums up the bond orders for the four bonds that link the Si atom at the origin with the
periodic images of itself in the primitive cell. A manual analysis of the multiplicities is required in such
cases, specifically: determine the number of bonds to periodic images of the same atom and divide
the bond order by that number. In cases where the bonds are not symmetry equivalent, you can
only obtain an average bond order.
Displaying computed charges, spins, and bond orders

Mulliken charge analysis is one of the most common types of charge analysis. The spin density matrix
and atomic overlap matrix are used to partition charges among the atoms. An alternative method of
charge partitioning is based on deformation density and produces so-called Hirshfeld charges.
To import and display computed atomic charges, spins, and bond orders, you need to have the
structure file (.xsd) and CASTEP output file (.castep) in a folder within the current project.

To display atomic charges or spins

2. Select Population analysis from the list of properties at the top of the dialog.
3. Make sure that the structure file from the CASTEP calculation is the active document.
4. Select the type of charges (Mulliken or Hirshfeld) that you wish to apply from the dropdown list.
5. Click the Assign charges to structure or Assign Mulliken spins to structure button, as appropriate,
to import the charge or spin data into the structure.
6. Right-click in the 3D Viewer and select Label from the shortcut menu to display the Label dialog.
7. Set the Object type to Atom, select Charge or Spin, as appropriate, from the Properties list, and
click the Apply button to display the charges or spins.
To display bond orders
2. Select Population analysis from the list of properties at the top of the dialog.
3. Make sure that the structure file from the CASTEP calculation is the active document.
4. Click the Assign Mulliken bond orders to structure button to import the bond order data into the
structure.
5. Right-click in the 3D Viewer and select Label from the shortcut menu to display the Label dialog.
6. Set the Object type to Bond, select BondOrder from the Properties list, and click the Apply button
to display the bond orders.
Calculating reaction kinetics

Reaction kinetics are described in terms of reaction rate coefficients. The rate coefficients are evaluated
in the transition state theory framework using information about the energies, geometries, and
vibrational frequencies of reactants, products, and transition state. In order to achieve better
agreement with experiment it might be advantageous to increase the reaction threshold value from the
DFT calculated one and to scale calculated harmonic frequencies to account for DFT deficiency and for
anharmonic effects.
The threshold correction can be applied either on a basis of more accurate ab initio calculations or based
on the comparison of calculated and experimental rate coefficients. It appears that a value in the region
of 6-7 kcal/mol describes DFT error adequately.
The recommended correction factors for DFT frequencies can be found at the NIST website for a variety
of exchange-correlation functionals: http://cccbdb.nist.gov/vibscalejust.asp.
To calculate reaction kinetics
2. Select Reaction kinetics from the list of properties.
3. Ensure that the desired 3D Atomistic collection document (seedname.xod) is the currently active
document.
4. Specify the temperature range of interest.
5. Check the Apply tunneling correction checkbox if the reaction involves motion of light elements.
6. Optionally specify a Threshold correction and a Vibrational frequencies scaling factor.
8. A new study table document, seedname.std, is created in the results folder.

Displaying the averaged potential chart for work function calculations

The CASTEP Analysis dialog can be used to generate plots of the change in electrostatic potential
through a slab, which is related to the energy required to remove an electron from the bulk into the
vacuum (the work function). The plots are created by averaging the electrostatic potential in the planes
perpendicular to the slab normal.
Note: Work function can only be calculated for structures constructed in a slab geometry so that they
contain atomic planes separated by a vacuum layer.
The averaged electrostatic potential is reported along the fractional coordinate of the unit cell in the
direction of the vacuum. The Fermi level is reported on the work function chart.
To create an averaged potential chart
2. Select Potentials from the list of properties.
3. Make the 3D Atomistic document containing the 3D periodic slab the active document.
4. Use the Results file selector to pick the results file.
5. Select the Potential field from the dropdown list.
6. Optionally check the View isosurface on import checkbox.
8. A new chart document, seedname Potential Profile.xcd, is created in the results
folder and becomes the active document. The selected potential field is imported into the 3D
Atomistic document and may be displayed as an isosurface.
Updating structure
Updating cell parameters and atomic coordinates after Geometry Optimization or a Dynamics run
should be the first step in the Analysis process.
Note: Structure updates happen automatically after a CASTEP job is completed and the results files
have been downloaded successfully. The description below is, therefore, only relevant for jobs which
were run in standalone mode and where the results files were transferred manually, or results files in
which the final structure produced by CASTEP has been manually modified and you wish to revert to
the unmodified form.
You can update the structure if the chemical composition (the number of atomic species and the
number of atoms of each kind) has not been changed since Materials Studio saved the structure in the
results folder. After the update, the cell parameters and atom coordinates are set to the values returned
by the CASTEP run in the (hidden) binary .check file.
To update the structure
2. Select Structure from the list of properties.
3. Ensure that the 3D model document to be updated is active.
4. Click the Update button.

Note: An error message is generated if the output .check file is incomplete, or if the chemical
composition of the model has been changed.
The Update button is enabled only if the output .check file is present and the active document is
the 3D model to be updated.
Creating a trajectory file

Note: A trajectory file, seedname.xtd, is automatically created when a CASTEP job is completed and
the results files have been downloaded successfully. The description below is, therefore, only relevant
for jobs which were run in standalone mode and where the results files were transferred manually.
The CASTEP server returns a number of ASCII text files to the client PC that can be used to create a
trajectory file for either a geometry optimization or a dynamics calculation. This trajectory is saved in a
hidden seedname Trajectory.trj file in the results folder.
This file contains complete information on the structure evolution, including changes in the energy,
temperature, stress, velocities and forces. Materials Studio does not currently provide tools for
analyzing this information. Although, it is possible to animate the trajectory.
Note: To perform statistical analysis of the results or to visualize atomic vectors (forces and velocities)
you can use Forcite Analysis.
To create a trajectory
2. Select Structure from the list of properties.
3. Ensure that the current document is either the 3D model in the results folder or the .castep file
of the corresponding calculation.
4. Click the Create button.
Displaying thermodynamic properties

Phonon calculations in CASTEP can be used to evaluate the temperature dependence of the energy,
entropy, free energy and lattice heat capacity of a crystal in a quasiharmonic approximation. These
results can be used to compare with experimental data (for example on heat capacity measurements),
to predict phase stability of different structural modifications, and so on (see Baroni et al., 2001). Warren
et al. demonstrated applicability of CASTEP to theoretical studies of phase transitions (Warren and
Ackland, 1996 and Warren et al., 1998).
An example of the CASTEP output for thermodynamic properties is shown in Figure 1. All energy-related
properties are plotted on one graph, and the calculated value of the zero-point energy is included. The
heat capacity is plotted separately on the right.
Note: The entropy is presented as an S*T product to allow comparison with the energy.

Figure 1. Thermodynamic properties of MgH2
Note: Thermodynamic properties calculated using the quasiharmonic approximation can be

inaccurate for temperatures comparable to the Debye temperature.
To create a thermodynamic properties chart
2. Select Thermodynamic properties from the list of properties.
3. Use the Results file selector to pick the appropriate results file (it should have a PhonDOS suffix).
4. Optionally, check Plot Debye temperature.
5. Select the desired temperature range.
7. A new chart document, seedname Thermodynamic Properties.xcd, is created in the results folder.
8. If Plot Debye temperature is checked, an additional chart document, seedname Debye
Temperature, is created in the results folder.
9. Optionally, click the Assign temperature factors to structure button to add temperature factor
information to the structure.

Chapter 3: CASTEP jobs
The topics in this section cover controlling and running remote CASTEP jobs, details of a sample remote
run, running jobs in standalone mode, and potential reasons why CASTEP might fail.
Using CASTEP job control

Materials Studio runs CASTEP jobs as background processes on a server. The following tools are
provided to setup and control the jobs:
Use the Job Control tab on the CASTEP Calculation dialog to select the gateway location and job
parameters for future jobs.
Use the Server Console application to add new servers and to monitor multiple jobs.
Use the Job Explorer to monitor multiple jobs.
For further information on using job control see the main job control and live updates help topics. Live
updates can be requested on the CASTEP Job Control Options dialog.
Running CASTEP jobs in parallel

CASTEP jobs can run in parallel on a server that supports MPI. The CASTEP interface uses the gateway
framework of Materials Studio to extract the relevant information for each gateway server. You can
select the number of cores to use, up to the maximum number available, as indicated by the text to the
right of the Run in parallel on control.
Note: It is recommended to use the number of cores which is commensurate with the number of k-
points in the calculation. You can determine the number of k-points by using the Display points...
button on the k-points tab of the CASTEP Electronic Options dialog.
CASTEP jobs can run in parallel using hybrid OpenMP/MPI parallelization. CASTEP uses the Materials
Studio gateway framework to extract the relevant information for each gateway server. You can select
the number of cores to use, up to the maximum number available, as indicated by the Run in parallel on
option on the Job Control tab of the CASTEP Calculation dialog. Furthermore, on Linux gateways you
can specify the desired number of threads to be used for each MPI process. The number of threads
must be commensurate with the number of cores requested and should not exceed the number of
cores on each execution host.
This functionality can substantially decrease the amount of memory required for a job (although it could
somewhat decrease speed).
Remote CASTEP jobs

CASTEP uses a client-server architecture that allows you use your PC to control calculations of the total
energy and electronic properties of a system or geometry optimizations and dynamics simulations of
structures running on a remote computer.
This separation of the client user interface from the server system, which runs the calculations, allows
you to use a high performance supercomputer from your Windows desktop PC. It also allows you to
make use of spare CPU cycles on other desktop PCs.
Execution of server code can be somewhat reconfigured. In particular, for Linux clusters it can be useful
to set MaxCoresPerProcessor to the actual number of cores per chip for homogeneous clusters. For

example, if a cluster node contains two 6-core chips, the value can be set to 6. This modification can
speed up parallel jobs for some architectures.
CASTEP jobs are controlled by input files that are generated by Materials Studio when you start a job.
CASTEP writes the results of the calculations to various output files, which are downloaded from the
server to the appropriate Materials Studio project when the job is completed.
CASTEP remote jobs run according to the standard sequence of processes described in A sample remote
job run with the differences explained in the Sample CASTEP run help topic.
A sample CASTEP run

Whether you perform a single-point energy calculation, minimize a structure, run a molecular dynamics
simulation, calculate elastic constants, or perform a transition-state search, the sequence of steps that is
executed to run a remote CASTEP job is always the same. When you click the Run button on the CASTEP
Calculation dialog, the steps described in A sample remote job run happen with the following
differences:
For Energy calculations, if
Update structure is checked: there is no effect, as no structural changes are associated with this task.
Update graphs is checked: Materials Studio creates a chart document called [seedname]
Energies.xcd, showing the total energy versus SCF iteration, and another chart document
called [seedname] Convergence.xcd, showing, on the logarithmic scale, the convergence of
the total energy versus SCF iteration.
Update textual results is checked: Materials Studio downloads a text file called Status.txt that
contains a summary of the calculation performed (task, DFT functional, energy cutoff for plane wave
basis set, electronic minimization method, system charge and spin, and so on), the SCF iteration
number, the total energy, and the total energy convergence (that is, the change from the previous
iteration).
For Geometry Optimization calculations, if
Update structure is checked: Materials Studio downloads a snapshot of the structure and modifies a
copy of the original structure accordingly.
Energies.xcd, showing the total energy versus optimization step, and another chart document
called [seedname] Convergence.xcd, showing, on the logarithmic scale, the total energy
change, the maximum displacement, the maximum force, and the maximum stress versus
optimization step.
basis set, electronic minimization method, system charge and spin, and so on), the SCF iteration
number, the total energy, the total energy convergence (that is, the change from the previous
iteration), the maximum displacement, the maximum force, and the maximum stress for the last
completed optimization step.
For Dynamics calculations, if

Constant.xcd, showing the constant of motion versus simulation time, and another chart
document called [seedname] Temperature.xcd, showing the temperature versus
simulation time. In addition, the chart document [seedname] Pressure.xcd is created if the
calculation is run using the NPH or NPT ensembles.
basis set, electronic minimization method, system charge and spin, and so on), the number of
completed dynamics steps, the temperature, and the constant of motion for the last completed
optimization step.
For Elastic Constants calculations, if
Update structure is checked: there is no effect, as no structural changes are associated with the
original structure. CASTEP performs an Energy calculation for the initial structure.
Energies.xcd, showing the total energy versus optimization step, and another chart document
called [seedname] Convergence.xcd, showing, on a logarithmic scale, the total energy
change, the maximum displacement, and the maximum force versus optimization step. These charts
refer to the structure currently being processed, as indicated by the index of the strain pattern and of
the strain magnitude for that pattern.
basis set, electronic minimization method, system charge and spin, and so on), a description of the
structure currently being processed (as indicated by the index of the strain pattern and of the strain
magnitude for that pattern), the number of completed optimization steps, the total energy, and the
total energy convergence (that is, the change from the previous iteration), the maximum
displacement, and the maximum force for the last completed optimization step.
For TS Search calculations, if
TSSearch.xcd, showing the total energy versus reaction coordinate. For each phase of the
transition-state search, a separate graph is displayed within the chart document.
Update textual results is selected: Materials Studio downloads a text file called Status.txt that
basis set, electronic minimization method, system charge and spin, and so on), a description of the
phase of the transition-state search currently being processed, the reaction path coordinate, the
total energy, the total energy convergence (that is, the change from the previous iteration), the
maximum displacement, and the maximum force for the last completed search step.
For Properties runs or for any other task where electronic structure properties (band structure, density
of states, or optical properties) are requested, textual updates are modified as follows.
When the CASTEP run enters the properties stage, the task description in the Status.txt file is
changed to either Eigenvalues (for band structure or density of states) or Eigenvalues + Optical
Properties (for optical properties). This file now contains a summary of the calculation, the number of
completed non-self-consistent iterations of the eigenvalues calculation, the maximum convergence of

electronic energies, and the maximum change in electronic energies on the last completed iteration for
any band or k-point.
Once the job has finished, Materials Studio will transfer the output files back to your PC, where you can
view and edit them, analyze the results, or use them for further calculations. Additional output files may
be generated or modified depending on the type of calculation you performed.
For Energy runs, Materials Studio downloads all the CASTEP output files.
For Geometry Optimization runs, Materials Studio downloads all the CASTEP output files, updates
the structure it has copied into the results folder to show the final geometry, and creates a trajectory
file, [seedname].xtd, that contains the history of the optimization process. The trajectory file
can be animated using the tools on the Animation toolbar.
For Dynamics runs, Materials Studio downloads all the CASTEP output files, updates the structure it
has copied into the results folder to show the configuration at the beginning of the dynamics run,
and creates a trajectory file, [seedname].xtd, that describes the molecular dynamics
calculation. The trajectory file can be animated using the tools on the Animation toolbar.
For Elastic Constants runs, Materials Studio downloads all the CASTEP output files for all strain
patterns and strain amplitudes.
For TS Search runs, Materials Studio downloads all the CASTEP output files, updates the structure it
has copied into the results folder to show the resulting configuration, and creates a trajectory file,
[seedname] .xtd, that contains the history of the optimization process. The trajectory file can
be animated using the tools on the Animation toolbar.
If a remote CASTEP job fails

Materials Studio checks most of the data and settings required to perform a CASTEP job prior to launch.
If it cannot start the job, error messages are generated detailing the reasons.
However, sometimes jobs may fail for reasons which cannot be checked prior to launch. In such cases,
more detailed information about the error may only be available in the [seedname].castep file
produced by the job or in the project log file. Other files stored in the job directory on the server, for
example, Castepexe.log, may also contain further clues. To view the server-side files, you can use
the Remote View facility of the Job Explorer.
Below is a list of the most common reasons for CASTEP jobs to fail. It may help you to identify and fix
any problems you have with your remote CASTEP jobs. For generic reasons for remote job failures
please consult the If a remote job fails help topic.
Tip: Select View | Project Log from the menu bar to see if any error or warning messages have been
reported.
Common reasons for a CASTEP job to fail to start
Server-side problems

Parallel CASTEP job fails with Error writing ... message under Linux.
Depending upon the options selected, CASTEP may use significant amounts of disk space to store
scratch files. Scratch files are created by each node during the execution of a parallel CASTEP job.
CASTEP uses the value of the environment variable GATEWAY_TMP as the location to be used to
save these files; this variable is set by share/bin/ms_vars.sbd and can be changed using the
gateway's web interface. You should ensure that the location that will be used on each node points
to a file system with at least 1 GB of free space. Note that the ./tmp setting for GATEWAY_TMP
corresponds to using the common file space on the head node, in the actual job directory, to store
the temporary files. This setting can have a detrimental effect on the performance of Linux clusters.
An additional problem may occur if the GATEWAY_TMP is set to the location on a shared disk
resource which is NFS mounted from the nodes. This mount should be done in a synchronous mode
using hard mounts.
Tip: It is important to identify the reason for the failure of a CASTEP job before taking any action. In
most cases, the error message produced will give a good indication of the reason for the failure. If the
error message indicates that the job failed, but does not provide specific reasons, check the
[seedname].castep file produced by the job or check the project log.
Running CASTEP in standalone mode

The most convenient way of running CASTEP is through the Materials Studio interface, which performs
all the preparatory tasks required to run a CASTEP job. However, in some circumstances, it may be
necessary to run CASTEP in standalone mode with a set of input files prepared elsewhere. For example,
you may wish to run a calculation on a server that has not been configured as a gateway, that is, a
computer that does not communicate with your Materials Studio client (perhaps because a firewall
prevents automatic file transfer and job launch).
For more general information on using standalone mode, see the Running jobs in standalone mode
help topic.
Generate the input files
CASTEP requires various input files that contain details of the calculation. More information about these
files can be found in the CASTEP file formats topic. You can create these files using a text editor, such as
WordPad on Windows or vi on Linux. However, because the information contained in the input files is
quite complex, you should use Materials Studio to generate them for you. You can create the required
files using the CASTEP Job Files dialog, see the Running jobs in standalone mode help topic for further
information.
Tip: Only the .param input file is displayed in the Project Explorer. The other input files are saved as
hidden files. You should ensure that your Windows folder settings allow you to view hidden files so
that you are able to see all of the files you need to copy to the server in order to run CASTEP. It may
also help to turn off the Windows option of hiding file extensions for known file types.
Transfer the input files to the server

If you generated the input files manually using a text editor on the server machine, then no file transfer
is required. However, if you generated the files on your PC using Materials Studio, you must transfer
them to the server before you can start the calculation.
If you are unable to access the hard drive on the server, you should use the File Transfer tool to transfer
files from the client to the server.

Execute the job

To assist you in running CASTEP in standalone mode, a batch/shell file called RunCASTEP is supplied. It
can be found in the directory in which the CASTEP executables are located, usually
etc/CASTEP/bin/ in the main Materials Studio directory. RunCASTEP scripts are used to start
CASTEP jobs in standalone mode. RunCASTEP.sh is provided for Linux servers, while
RunCASTEP.bat is provided for Windows servers.
Usage:
RunCASTEP.sh [-h] [-np number of cores] [-nt number of threads] [-q queue name]
seedname (Linux)
or
RunCASTEP [-h] [-np number of cores] [-q queue name] seedname (Windows)
Argument Description
-h Displays the help text.
-np Specifies the number of cores on which to run CASTEP. When this option is
not specified a single core is used.
number of cores The number of cores to use.
-nt Specifies desired number of threads. When this option is not specified a
single thread for each process is used.
number of The number of threads to use.
threads
-q Submits the job to the specified queue.
queue name The name of the queue on which to run the job.
seedname The seed used to identify the set of CASTEP input and output files. The input
files should be present in the directory in which the CASTEP script is started.
If you wish to calculate properties, you should execute the script with all the seednames as parameters
for the RunCastep.sh:
RunCASTEP.sh -np 4 seedname seedname_BandStr seedname_DOS seedname_Optics
Note: By default large seedname.check files are removed after the execution to save space. In
most cases the seedname.castep_bin files are enough to restart the calculation. However, if
check files are needed they can be requested by adding the following command:
-extraoptions KeepCheckFiles:Yes
For example:
RunCASTEP.sh -extraoptions KeepCheckFiles:Yes seedname
Download the output files from the server

When the CASTEP calculation is complete, you must transfer the output files back to your PC for analysis
in Materials Studio. See Running jobs in standalone mode for further information.

To transfer the output files back to your PC

1. Transfer the output files to the client PC using either copy and paste or the File Transfer tool.
2. A complete list of the output files that are generated and descriptions of their contents can be
found in the CASTEP file formats topic. All of the files, seedname.*, seedname_BandStr.*,
seedname_DOS.*, seedname_Optics.*, seedname_PhonDOS.*, seedname_
PhonDisp.*, and seedname_Subset*.*, should be downloaded from the server.
Tip: After you have transferred the output files, you may wish to modify their attributes such that all
of them except the .castep file are hidden files. This avoids cluttering up the display in the Project
Explorer.
Tip: If you have transferred files into a Materials Studio project folder, but you cannot see them in
the Project Explorer, try using the Refresh button to update the Project Explorer.
Open the output files in Materials Studio

Provided that you have transferred the correct files from the server to your PC and stored them in a
folder in a Materials Studio project, you should be able to make use of the CASTEP analysis options
described in the topic Analyzing CASTEP results. Specifically, you can open the 3D Atomistic document
containing the starting structure and update it, create a trajectory document and animate it, visualize
volumetric properties, calculate DOS and optical spectra, and plot band structure.
CASTEP file formats

The CASTEP server program is a file-based application. It requires input files and produces a number of
output files. The precise number and type of output files produced depends on the details of the
CASTEP job being performed.
The table below summarizes information on the format and purpose of all the major file types, and
provides links to further information.
File type Input or Brief description

Output
.param Input General input file (text)
.cell * Input Structure input file (text)
.castep Output Report on the calculation (text)
.check, Output Charge density, wavefunctions, structure, and so on (binary)
.castep_bin *
.bands * Output Eigenvalues (text)
.cst_esp * Output Electrostatic potentials (binary)
.geom * Output Geometry optimization trajectory data (text)
.md * Output Molecular dynamics trajectory data (text)
.ts * Output Transition state search trajectory data (text)
.phonon * Output Phonon data (text)

File type Input or Brief description

Output
.pdos_weights Output Weights required to calculate PDOS (binary)
*
.cst_ome * Output Matrix elements required to calculate optical properties (binary)

.elf * Output Electron localization function, ELF (binary)
.bib Output Bibliography file in BibTeX format (text)
.otfg * N/A Information required for generating pseudopotential files on the fly
stored on the client (text)
.tddft Output Results of a CASTEP calculation of excitations in the time-dependent
DFT approach
* These files are hidden by default, so they will not appear in the Materials Studio Project Explorer; these
files are only visible in the Windows File Explorer if Windows on your machine is configured to show
hidden files.
CASTEP file formats - PARAM

The .param file contains all of the control parameters required to run a CASTEP job, including the type
of calculation, the charge, the spin state, and convergence tolerances. The file consists of lines
containing keywords and associated values.
A .param file is generated by Materials Studio when you launch a calculation or when you click the
Save Files button on the CASTEP Job Files dialog. Job options selected using the interface appear as
keywords in the resulting .param file.
Under certain circumstances, you may wish to manually add keywords to a .param file. The procedure
is described in the topic Running CASTEP in standalone mode.
The following rules govern keywords in the .param file:
Keywords may appear in any order.
The keywords and values are case- and punctuation-insensitive.
Only one keyword and its options may appear on a line.
Keywords that do not appear in the .param file are set to their default values.
Units may be specified for physical quantities.
Note: Recognized units and their identifiers are listed in the UNIT keyword topics. If no units are
specified, the default units will be assumed.
Comment lines (those beginning with #, ;, ! or COMMENT) and blank lines are ignored.
Keywords and their values are fully described in the topic CASTEP keywords.
CASTEP file formats - CELL

The .cell file contains geometry information, including cell parameters, atomic coordinates, and k-
point coordinates and weights. The file consists of lines containing keywords and data blocks, and
associated values.

A .cell file is generated by Materials Studio when you launch a calculation or when you click the Save
Files button on the CASTEP Job Files dialog.
Under certain circumstances, you may wish to manually add keywords to a .cell file. The procedure is
described in the topic Running CASTEP in standalone mode.
The following rules govern keywords and data blocks in the .cell file:
Keywords and data blocks may appear in any order.
The keywords, data blocks, and values are case- and punctuation-insensitive.
Only one keyword and its options may appear on a line.
Data blocks are preceded by %BLOCK <keyword>, followed by a series of data lines, and
terminated by %ENDBLOCK <keyword>.
Keywords and data blocks that do not appear in the .cell file are set to their default values.
Units may be specified for physical quantities.
Note: Recognized units and their identifiers are listed in the UNIT keyword topics. If no units are
specified, the default units will be assumed.
Comment lines (those beginning with #, ;, ! or COMMENT) and blank lines are ignored.
Keywords and their values are fully described in the topic CASTEP keywords.
CASTEP file formats - CASTEP

The .castep file contains the numerical output of a CASTEP job in ASCII format. The header describes
the settings used, followed by the calculation results.
CASTEP file formats - binary checkpoint files

The .check and .castep_bin files contain the numerical output of a CASTEP job in binary format.
The difference between the two files is that the .check file stores electronic wavefunctions in addition
to all other information (calculation parameters, structure, electron density, electronic, and vibrational
properties) and can become very large for large systems.
At least one of these files is required by the Materials Studio client to analyze CASTEP results. The
CASTEP module in Materials Studio allows you to choose which of the two binary files to download after
job execution.
Note: Visualization of orbitals or of STM images requires information about electronic wavefunctions,
hence the .check file is always downloaded if any of these properties were requested.
CASTEP file formats - BANDS

The .bands file contains electronic eigenvalues for all k-points in a CASTEP job. The data in this file are
used for band structure plotting and optics, DOS, and PDOS calculations.
The file has the following format:
The eigenvalues are given in atomic units. The k-points are specified using fractional coordinates, which
are followed by the corresponding k-point weight.
CASTEP file formats - CST_ESP

The .cst_esp file contains the electrostatic potentials output from a CASTEP job.

CASTEP file formats - task-specific files

CASTEP produces additional output files only when certain tasks are selected:
.geom - Geometry optimization
.md - Molecular dynamics
.ts - Transition state search
These files contain trajectory information and have the following format:
-1.82539879E+002 -1.82539879E+002 <-- E
Values are always specified in atomic units and one of the following letter codes will be present:
E - total energy and enthalpy
T - temperature
R - atomic coordinates (Cartesian)
h - cell matrix
hv - derivatives (velocities) of the cell matrix
F - forces
V - velocities
S - stress tensor
P - pressure
CASTEP file formats - PHONON

The .phonon file contains phonon frequencies and eigenvectors for all q-vectors in a CASTEP phonon
calculation. The data in this file are used for phonon dispersion plotting, phonon DOS, and projected
(partial) phonon DOS calculations. Phonon frequencies are always given in wavenumbers (cm-1).
CASTEP file formats - TDDFT

The .tddft file contains detailed information about the results of a CASTEP calculation of excitations in
the time-dependent DFT approach.
The header contains information about the structure, this block is followed by the representation of
excited states as a superposition of Kohn-Sham one-electron bands. The overlap between occupied and
unoccupied states gives a useful indication of the degree of charge transfer in every given excitation (if
the value is significantly lower than 1.0, the TD-DFT description might be inaccurate since it does not
take charge transfer into account).
The final section contains spectroscopic data; excitations energy, singlet or triplet character, level of
convergence, and transition dipoles (the position operator between the ground-state wavefunction and
the first order response wavefunction for the Nth excited state from TDDFT, ). The
transition dipole is projected onto the Cartesian axes. The character can be marked as "spurious" to
reflect the fact that there are mathematically valid solutions to the linear-response TDDFT eigenvalue
problem that are not physical (Heßelmann and Görling, 2009). These are solutions that provide a pure
Kohn-Sham orbital transition, with no contribution from the exchange-correlation action. In terms of
observables, the matrix elements will be zero (numerically so for computed quantities), and therefore
harmless unless you want to select a specific state, for example for a structure optimization.

CASTEP file formats - PDOS_WEIGHTS

The .pdos_weights file contains the weights that are required to generate partial densities of state
(PDOS), based on the results of a CASTEP job.
CASTEP file formats - CST_OME

The .cst_ome file contains the matrix elements for electronic interband transitions that are required
to generate the dielectric function and other optical properties, based on the results of a CASTEP job.
This is a binary file which contains the array of matrix elements; M(band1,band2,coord,k,spin). The loop
is over the number of bands (band1, band2), x, y, z components (coord), k-points (nk), and spins (ns).
CASTEP file formats - ORBITALS

The .orbitals file contains the electronic wavefunctions from a CASTEP job. This file is created only
for band structure or optics runs; the wavefunctions for all other types of CASTEP calculations are stored
in the .check file. The .orbitals file is required to carry out analysis of orbitals and of the STM
profile based on the output of band structure or optics calculations.
CASTEP file formats - CHDIFF

The .chdiff file contains the electron density difference calculated as part of a CASTEP job. The
density difference is evaluated by subtracting the sum of the atomic densities from the total electron
density of the system.
CASTEP file formats - ELF

The .elf file contains the electron localization function output from a CASTEP job.
CASTEP file formats - OTFG

The information required for generating CASTEP pseudopotential files on the fly is stored on the client in
the files with the .otfg extension. These files are intended for the use on the client only, they are not
expected to be transferred to the gateway server. The purpose of these files is to create a correct string
in the SPECIES_POT block in .cell file.
The .otfg files can be edited manually, and new files with this extension can be created and stored in
the Resources\Quantum\Castep\Potentials folder on the client. The most likely purpose for the editing
would be to change the default core radius in order to create a softer (bigger core radius) or a more
accurate and hard (smaller core radius) version of a pseudopotential for a given element. Occasionally,
when core holes are used for some elements different settings are more appropriate.
The latest set of OTFG settings for ultrasoft pseudopotentials has been developed in order to minimize
the error with respect to fully converged all-electron DFT calculations. The error achieved by this set is
0.4 meV/atom, which puts CASTEP among the most accurate pseudopotential codes available. A full
definition of the test framework and the meaning of the error is given by Lejaeghere et al. (2014), and on
the website of the Delta project: http://molmod.ugent.be/deltacodesdft. The files that correspond to
this set have the _2017R2 suffix . This is the recommended set of OTFG ultrasoft potentials. Files with
the _2017R2ncp suffix are recommended when norm-conserving potentials are required (this set has
a 1.1 meV/atom error in the Delta project tests). In addition, a set of "high throughput" ultrasoft OTFG
settings is available for scripting; this QC5 set generally requires lower cutoff energy and offers faster but
less accurate calculations (1.9 meV/atom error in the Delta project tests).
See Prof. David Vanderbilt's website on pseudopotential generation for more information:
http://www.physics.rutgers.edu/~dhv/uspp/
The format can be described as:

The order of the blocks and of single lines with keywords in the file is irrelevant.
The order of the lines inside the BLOCK constructs is irrelevant.
The separator between the keyword and the value can be any of the designated separators: "=",":",
tab, space.
The case of the keyword is irrelevant.
The comments are allowed after the value as long as they are separated by at least one designated
separator.
The compulsory fields are the ones in red in the description above.
The string fields have to be enclosed in single quotation marks.
The energy shifts, CHANNEL_INFO_SHIFT, can be given either as shifts relative to the atomic
eigenvalues or as an absolute value (in which case, the value should be preceded by VAL and a
designated separator).
The level shifts, CHANNEL_INFO_LEVELSHIFT, are artificial shifts of atomic eigenvalues relative to their
DFT positions. Such shifts can be used to correct DFT error in relative positions of bands in a solid
state calculation, see Profeta et al. (2004) for details.
Information about multiple projectors in the CHANNEL_INFO lines should be separated by "&&", and
there should be also at least one of the designated separators on either side of the "&&" construct.
CHANNEL_INFO_TYPE, CHANNEL_INFO_SHIFT and CHANNEL_INFO_BETA_RC values within a
CHANNEL_INFO block are all optional; if either of these entries is omitted CASTEP will use the default
values for the respective property. The default setting is to use two ultrasoft projectors, using atomic
eigenvalues as reference energies, and using BETA_RADIUS value specified elsewhere in the .otfg
file.
If two or three out of CHANNEL_INFO_TYPE, CHANNEL_INFO_SHIFT and CHANNEL_INFO_BETA_RC
fields are present, then each of these fields should contain the same number of values.
A block enclosed in STARTCOMMENT and ENDCOMMENT tags can be inserted anywhere in the file;
its contents are ignored and can be used to keep a record of, for example, convergence testing and
validation studies.
The only value currently allowed on the COMPATIBILITY line is 'compat7'. The generator has been
improved in the 8.0 release, so that it produces slightly different (although functionally equivalent)
pseudopotential from the same input. The COMPATIBILITY option has been added to all 00.otfg
files to ensure compatibility with the earlier releases.
Note: COARSE, MEDIUM and FINE values are used by the CASTEP GUI in order to determine the
cutoff energy for the calculations carried out at the specified level of accuracy. If you are generating a
new file, you would have to carry out the convergence testing to determine the appropriate values
for the new potentials.
In order to ensure that the OTFG for core holes is appropriate some conditional settings have been
appended for certain elements, in a section which is only used when core holes are requested. If core
holes are not being used in the calculation the CORE_HOLE_INFO keywords are ignored and the
preceding settings are used.
Reaction Kinetics Study Table

The results of the reaction rate calculation are collected in a study table which contains the following
tabs:

Summary - contains a summary of the results, reporting the main parameters of the calculation, fit
coefficients, and root-mean-square error (RMSE) which is calculated for ln(k(T)). If the fit parameters
(also shown on the Graphs tab) produce too high n, or Ea becomes negative, the corresponding lines
in the study table are highlighted in red.
Structures - contains the collection document representing the entire reaction as well as one
atomistic document for each of the reactants and products.
Graphs - contains the temperature dependence of the reaction rates coefficients (k(T)) for forward
and backward reactions together with equilibrium constants. It also contains results of the fit using
Arrhenius form (see Kinetics constants theory) with temperature T0 = 298.15 K together with
standard Arrhenius form (n = 0, the temperature independent pre-exponential coefficient).
Partition Function - contains the calculated partition functions for reactant(s), product(s), and
transition state.

Chapter 4: Theory in CASTEP
The following topics provide specific details about the theory behind CASTEP.
CASTEP background theory

This section provides information specific to the implementation of DFT in the CASTEP program. A
general overview of DFT is provided elsewhere. The general overview provides information on the
concepts of charge density, DFT functionals, the SCF procedure, and band structures, which are
applicable to any computational implementation of DFT. The application of dispersion corrections to
DFT is also described.
In contrast, this section provides background information on aspects of DFT that are specific to CASTEP.
The CASTEP program provides a robust and efficient implementation of DFT which is based on the
following concepts:
Pseudopotential description of the electron-ion interaction
Supercell approach with periodic boundary conditions
Plane wave basis set
Extensive use of fast Fourier transform (FFT) for evaluation of the Hamiltonian terms
Iterative schemes for the self-consistent electronic minimization
Implementation of the most popular DFT expressions for the exchange-correlation functional,
including the screened and exact exchange schemes.
Some of these topics are expanded on in this section. More detailed information can be found in the
links listed at the end of this topic.
Supercell approach
CASTEP is based on a supercell method, wherein all studies must be performed on a periodic system,
even when the periodicity is superficial. Thus, for example, a crystal surface must be represented by a
finite-length slab (Figure 1). Similarly, to study molecules it is necessary to assume that they are in a box
and treat them as periodic systems. There is no limitation on the shape of the supercell.

Figure 1. Schematic representation of the supercell calculation of a small molecule adsorption on a surface
The main advantage of imposing periodic boundary conditions relates to Bloch's theorem, which states
that in a periodic system each electronic wavefunction can be written as a product of a cell-periodic part
and a wavelike part (Payne et al. 1992):
Eq. CASTEP 1
The cell periodic part, ψ, can then be expanded using a basis set consisting of a discrete set of plane
waves whose wave vectors are reciprocal lattice vectors of the crystal:
Eq. CASTEP 2
Therefore, each electronic function can be written as a sum of plane waves, exp[i(k+G)•R]. Advantages
and technical details of the plane wave basis set are described in a separate section.
Among the major gains is the simplified form of the Kohn-Sham equations:
Eq. CASTEP 3

In this form, the kinetic energy is diagonal, and the various potentials (electron-ion, Hartree, exchange-
correlation) are described in terms of their Fourier transforms.
Another advantage of the plane wave basis set is the ease of calculating derivatives of the total energy
with respect to atomic displacements (that is, stresses and forces are computationally cheap in this
approach), so that efficient geometry optimization and molecular dynamics schemes can be
implemented. It is also straightforward to study and improve convergence of plane-wave basis set
calculations, as there is a systematic way of adding more basis functions.
However, there is an additional cost to using the supercell approach for systems that lack periodicity in
three dimensions inherently (isolated molecules, defects in solids, surfaces, and so on). In a study of a
single defect, for example, the properties of an infinite array of defects (Figure 2) would always be
calculated. Therefore, it is essential to introduce enough separation between artificial images of such
nonperiodic objects to ensure that there is no appreciable interaction between them. The situation is
similar for surface calculations that are carried out in a slab geometry. The vacuum layer should be
sufficiently thick to eliminate artificial interactions between the slabs.
Figure 2. Schematic representation of the supercell calculation of a substitutional impurity in a bulk
Fast Fourier transforms (FFT) in CASTEP

One of the major computational steps in CASTEP is the calculation of the product of the Hamiltonian
with a wavefunction, Hψ. It has been shown above that the kinetic energy operator of the Hamiltonian
has a diagonal representation in reciprocal space. The same is true of the Hartree operator and of the
local pseudopotential operator. Exchange-correlation potential, on the other hand, has a diagonal
representation in real space. This means that there is a need for an efficient way of transforming various
entities (wavefunctions, potentials, search directions) from real to reciprocal space and back. FFT

provide this, so that the gain due to the evaluating various parts of the Hamiltonian in their "natural"
representations is not offset by the cost of the transformation.
Exchange-correlation functionals in CASTEP

CASTEP implements a number of exchange-correlation functionals: local (LDA), gradient-corrected (GGA),
and fully nonlocal (based on the exact and screened exchange formalism).
Local exchange-correlation functionals in CASTEP
The exchange-correlation energy is given by Eq. DFT 7. There is only one local functional provided in
CASTEP, the Perdew and Zunger (1981) parameterization of the numerical results of Ceperley and Alder
(1980), CA-PZ.
This particular prescription for the local representation of the exchange-correlation potential is
considered to be one of the most accurate descriptions available (Srivastava and Weaire, 1987).
Gradient corrected exchange-correlation functionals in CASTEP
The so-called nonlocal or gradient-corrected functionals depend on dρ/dr as well as on ρ. This provides a
considerable increase in the accuracy of predicted energies and structures, but with an additional cost.
The nonlocal functionals available in CASTEP include:
Name Description Reference

PW91 Perdew-Wang generalized-gradient approximation, PW91 Perdew and Wang
PBE Perdew-Burke-Ernzerhof functional, PBE Perdew et al.
RPBE Revised Perdew-Burke-Ernzerhof functional, RPBE Hammer et al.
WC More accurate GGA functional, based on a diffuse radial cutoff for Wu and Cohen
the exchange hole in real space and the analytical gradient
expansion of the exchange energy for small gradients
PBEsol A version of the PBE functional that improves equilibrium Perdew et al.
properties of densely packed solids and their surfaces
BLYP Becke exchange, Lee-Yang-Parr correlation Becke; Lee, Yang, Parr
The PBE functional has been designed to give essentially the same results as the PW91 functional but it
is more robust in systems with rapidly varying electron density. The RPBE functional has been designed
specifically to improve the DFT description of the adsorption energies of molecules on metallic surfaces
(for a detailed comparison of these three functionals when applied to surface science problems see
Marlo and Milman, 2000). One of the latest developments, PBEsol functional, is explicitly designed to
improve the first-principles gradient expansion for exchange over a wide range of density gradients, and
hence to improve the description of equilibrium properties of densely packed solids and their surfaces.
All gradient-corrected functionals in CASTEP are implemented according to the method described by
White and Bird (1994). The application of gradient-corrected exchange-correlation functionals in total-
energy calculations using a plane-wave basis set is less straightforward than in localized basis set
approaches (used in other programs such as DMol3). The usual form of the exchange-correlation
potential includes gradients whose calculation requires the use of a high-quality representation of the
density which is computationally expensive in both memory and time. These problems are overcome by
defining an exchange-correlation potential for the discrete set of grid points consistent with the
discretized form of the exchange-correlation energy that is used in plane-wave total-energy calculations.

This potential is calculated exactly on the minimum fast Fourier transform grid and gives improved
convergence and stability as well as computational efficiency.
Meta-GGA functional
In addition to the generalized gradient (GGA) functionals, which depend on the local density and its
gradient, CASTEP can handle functionals that depend on the kinetic energy density. The current
supported functional is RSCAN (Bartók and Yates, 2019), which is an improved regularized version of the
SCAN ("Strongly Constrained and Appropriately Normed") functional developed by Sun et al., 2016.
Meta-GGA functionals are considered to be more accurate than pure GGA, and the cost of such
calculations is significantly lower than for nonlocal functionals.
The SCAN functional satisfies all known constraints that a semi-local functional can satisfy, and the
remaining free parameters are fitted to reproduce exact or accurate reference values, or norms, of
exchange and correlation energies.
The RSCAN modification eliminates the unphysical divergence of the exchange-correlation potential,
which occurs in some free atoms, and fixes the feature of the switching function in SCAN, which
introduces rapidly oscillating regions in the exchange-correlation potential. These improvements are
necessary to make the SCAN functional usable in the context of robust pseudopotential generation.
CASTEP's implementation has shown that RSCAN is transferable and accurate for a broad range of solid
state and molecular systems.
Note: Currently, there are limitations on the use of meta-GGA in CASTEP. The meta-GGA functional is
not compatible with DFT-D corrections, spin-orbit coupling, J-coupling , linear-response phonons, or
polarizability calculations. The formalism cannot be used with mixture atoms. Only on the fly
generated pseudopotentials can be used.
Nonlocal exchange-correlation functionals in CASTEP

Kohn-Sham schemes based on LDA and GGA functionals have a common feature: they underestimate
the band gap substantially. This does not affect the accuracy of the description of the total energy and
related properties of crystals and molecules (equilibrium structure, vibrational spectra, elastic constants,
and so on). However, an accurate description of the details of the electronic structure is often required
to understand the properties of semiconductors and insulators. Then a DFT error of up to 50% in the
calculated band gap energy becomes unacceptable.
It is possible to correct for the DFT band gap error by introducing an empirical scissors correction, which
is effectively a rigid shift of the conduction band with respect to the valence band. This approach
produces satisfactory results for such properties as optical spectra, provided the experimental band gap
is accurate. The scissors operator scheme is very difficult to use in predictive studies and in the context
of band gap engineering, when there is little or no experimental information about the electronic
structure. In addition, the scissors operator approach does not help when an improvement in the
description of the electronic structure of metallic systems is required.
There are a wide variety of techniques designed to deal with the band-gap problem in DFT. Most of
them are exceedingly complex and time consuming. One of the most practical solutions is the so-called
screened exchange, or sX-LDA scheme, developed in the context of the generalized Kohn-Sham
procedure (Seidl et al., 1996). Generalized Kohn-Sham schemes allow one to split the exchange
contribution to the total energy into a screened, nonlocal and a local density component.
The following generalized Kohn-Sham schemes are implemented in CASTEP:

HF: exact exchange, no correlation

HF-LDA: exact exchange, LDA correlation
sX: screened exchange, no correlation
sX-LDA: screened exchange, LDA correlation
PBE0: combination of PBE functional with a predefined amount of exact exchange (Adamo and
Barony, 1998)
B3LYP: combination of Hartree-Fock exchange with DFT exchange-correlation (Becke, 1993)
HSE03: hybrid functional based on a screened Coulomb potential (Heyd et al., 2003)
HSE06: similar to HSE03, but with optimized screening parameters (Krukau et al., 2006)
Tip: The sX-LDA or HSE06 scheme is recommended for band gap calculations.
The implementation of screened exchange in CASTEP follows closely the recipe suggested by Seidl et al.
(1996). The Thomas-Fermi screening function is used (the case of zero screening length, k TF,
corresponds to the exact exchange formalism).
CASTEP provides a number of schemes for evaluating the screening length. The most straightforward to
use is average density. This is a reasonable approach for bulk solids, but not for systems with large
amounts of vacuum in the cell, for example molecules, surfaces, porous materials, and so on.
Alternatively, you can use the k TF value associated with the self-weighted average density of the system.
The self-weighted average is given by the integral of the density squared divided by the integral of the
density. This removes the problems connected with large regions of vacuum. Otherwise, you can
evaluate the self-weighted average of the screened exchange energy density.
Nonlocal functionals have certain limitations compared with LDA and GGA functionals. For example,
there is no known analytical expression for the stress tensor components in the exact exchange
formalism. Thus, none of the fully nonlocal potentials can be used to optimize the unit cell of a crystal or
to perform NPT/NPH dynamics (only sX-LDA, HSE03, or HSE06 functionals support stress calculations). It
is also possible that the optical properties calculated using these functionals may be inaccurate. This
problem is related to the introduction of a fully nonlocal component of the Hamiltonian. The addition of
a nonlocal potential breaks the usual expressions for transforming the optical matrix element from the
position operator to the momentum operator, because the commutator with the Hamiltonian becomes
exceedingly complex (Asahi et al., 1999). However, even with the significant computational overhead of
the screened exchange formalism, it provides a state of the art scheme for predictive studies of
electronic and optical properties of crystals.
Tip: Nonlocal functionals are currently implemented only for norm-conserving potentials, not for
ultrasoft ones.
Note: There is an important difference between standard DFT calculations with local exchange-
correlation potentials and the nonlocal exchange case. The potential used in the latter scenario
depends on the SCF k-points, while in the former case, the potential depends only on electron
density. This difference can make all properties calculations a lot more expensive in terms of memory
usage and CPU time, so it is advisable to limit the number of SCF k-points that you use in such
situations. This is particularly relevant for small unit cells, where the default settings may generate a
very large k-point set.
Spin Orbit Coupling

Spin orbit coupling between the electron's spin and its orbital angular momentum couples the direction
of spin with the underlying lattice. This is a relativistic effect that increases in magnitude with the nuclear

charge, Z. For materials with heavy elements a scalar relativistic treatment (that is, one that neglects the
spin orbit interaction) is insufficient to model the electronic band structure. In magnetic systems, the
spin orbit coupling introduces a preferential direction (or set of directions) for the spin density.
The inclusion of spin orbit coupling is required for the prediction of many physical properties; for
example, effective masses in semiconductors (modeling light and heavy holes); the anomalous Hall
effect; Berry curvature; topological insulators, and magnetoelectrics.
In the plane waves and pseudopotential model, only the pseudized valence electrons are explicitly
modeled. These electrons have a velocity, v << c, and as such the standard (non-relativistic) Kohn-
Sham (KS) equations are appropriate. The spin orbit coupling is included using j-dependent
pseudopotentials developed based on work by Dal Corso et al. (2005). These pseudopotentials act on KS
spinor wavefunctions and an electron density with a vector spin at each grid point.
DFT+U (LDA+U)
DFT can only give access to the ground state properties of a system, even if the exact exchange-
correlation potential were known. For electronic excitations to be modeled Kohn-Sham equations must
be substituted by the Dyson equation, where instead of the unknown exchange-correlation potential
the energy dependent self energy operator is used. This operator often can be represented by the local
and energy-independent exchange-correlation potential, in which case one recovers the Kohn-Sham
equations for one-electron excitations. However, this approach is not appropriate for a large class of
compounds, so-called correlated systems. These systems require a mixture of the Hubbard model
theory and DFT. The most popular implementation is known as the DFT+U method as introduced by
Anisimov and co-workers (1991).
The CASTEP implementation of DFT+U adopts a simplified, rotationally invariant approach (Cococcioni
and de Gironcoli, 2005, Dudarev et al., 1998). The only external parameter needed for this approach is
the effective value of the on-site Coulomb parameter, U, for each affected orbital. This parameter can be
calculated theoretically (Cococcioni and de Gironcoli, 2005). However, experience shows that the best
results are achieved when the U parameter is allowed to vary depending on the property of interest.
CASTEP therefore does not calculate the value of U but uses it as an input parameter.
Symmetry in CASTEP
The original ideas of utilizing space group symmetry in plane-wave total energy calculations can be
traced back to the k290 package (Kunc et al., 1985). The importance of this issue for achieving high
performance has long been recognized. Often a high symmetry system has a fairly small unit cell. This
means that the Brillouin zone is quite large and a high number of k-points are therefore required for
efficient Brillouin zone sampling. This number can be greatly reduced if it is recognized that the
contributions to the charge density from wavefunctions with k-vectors that are related by symmetry are
related. It is then sufficient to use only one k-point from each star of symmetry-related points. Because
the cost of a CASTEP calculation increases linearly with the number of k-points, any symmetry-related
reduction in the number of k-points gives a direct computational speedup.
Space group symmetry is also used in CASTEP during geometry optimization. Forces on atoms, the
stress tensor and consequently atomic displacements and changes in the cell parameters, are always
symmetrized so that the space group symmetry can never become lower during a CASTEP calculation.
However, CASTEP does not perform symmetry analysis. Instead, it uses symmetry information provided
by Materials Studio.
Pseudopotentials
The concept of a pseudopotential is a crucial one for plane-wave total energy methods since the
alternative full Coulomb potential of the electron-ion interaction decays too slowly to be accurately

represented by a small number of Fourier components.

Another way of looking at the problem is to analyze wavefunctions. Consider a solid as a collection of
valence electrons and ion cores. The ion cores contain nuclei and tightly bound core electrons. The
valence-electron wavefunctions are orthogonal to core-electron wavefunctions. All-electron DFT
methods treat core and valence electrons on an equal footing. In the pseudopotential approach ion
cores are considered to be frozen. This means that properties of molecules or solids are calculated on
the assumption that the ion cores are not involved in chemical bonding and do not change as a result of
structural modifications.
All-electron wavefunctions of valence electrons exhibit rapid oscillations in the core region in order to
satisfy the orthogonality constraint. It is impractical to represent such functions using plane waves as
the size of the basis set would be prohibitive. The pseudopotential approximation replaces core
electrons and the strong Coulomb potential by a weaker pseudopotential that acts on a set of pseudo
wavefunctions. This potential can be represented with only a small number of Fourier coefficients.
Pseudo wavefunctions ideally should have no nodes inside the core regions and thus they only require a
small basis set. It is now well known that the combination of the power of plane wave technology and
the pseudopotential concept is extremely useful for the description of chemical bonding (for a review
see Srivastava and Weaire, 1987).
Traditionally, pseudopotentials are constructed so as to reproduce faithfully the scattering properties of
the full ionic potential. The phase shift produced by the ionic core is different for each angular
momentum component (s, p, d, and so on) of the valence wavefunction. Thus, the scattering from the
pseudopotential must be angular momentum dependent. The most general form for a pseudopotential
is:
Eq. CASTEP 4
where |lm> are the spherical harmonics and Vl is the pseudopotential for angular momentum l. A
pseudopotential that uses the same potential in each angular momentum channel is called a local
pseudopotential. Local pseudopotentials are computationally much more efficient than a nonlocal ones,
however, only a few elements can be described accurately using local pseudopotentials.
An important concept in the pseudopotential applications is the degree of hardness of a
pseudopotential. A pseudopotential is considered soft when it requires a small number of Fourier
components for its accurate representation and hard otherwise. Early development of accurate norm-
conserving pseudopotentials quickly showed that the potentials for transition metals and for first row
elements (O, C, N, and so on) turn out to be extremely hard (Bachelet et al., 1982; Kerker, 1980 ). Various
schemes have been suggested to improve convergence properties of norm-conserving
pseudopotentials (Troullier and Martins, 1991). Norm-conserving potentials in CASTEP are generated
using the kinetic energy optimization scheme developed by Lin et al., (1993) and Lee (1996).
A more radical approach was suggested by Vanderbilt (1990), which involves relaxing the norm
conservation requirement in order to generate much softer pseudopotentials. In the ultrasoft
pseudopotential scheme the pseudo-wavefunctions are allowed to be as soft as possible within the core
region, so that the cutoff energy can be reduced dramatically. Ultrasoft potentials (USP) have another
advantage besides being much softer than the norm-conserving potentials. The generation algorithm
guarantees good scattering properties over a pre-specified energy range, which results in much better
transferability and accuracy of the pseudopotentials. USP usually also treats shallow core states as
valences by including multiple sets of occupied states in each angular momentum channel. This also
adds to high accuracy and transferability of the potentials, although at a price of computational
efficiency.

Transferability is the main benefit of the pseudopotential technique over all electron DFT
implementations. Pseudopotentials are constructed from a fixed electronic configuration of an isolated
atom or ion and thus they reproduce the scattering properties of a nucleus in that particular
configuration. They can also be used reliably for any other atomic configuration or in various solid-state
environments due to the way in which they are generated, which guarantees the correct scattering
properties over a wide energy range. An example of the accuracy that can be achieved across a number
of structures and chemical environments is given by Milman et al. (2000).
Nonlocal pseudopotentials, even in their most efficient separable representation (Kleinman and
Bylander, 1982), still consume a large share of the computational time in pseudopotential total-energy
calculations. In addition, the cost of applying nonlocal pseudopotentials in reciprocal space increases
with the cube of the number of atoms. Therefore, it becomes one of the dominant operations for large
systems. The nonlocality of the pseudopotential, however, extends only over the region occupied by
the core of the atom. As the core region is relatively small, especially if the system has a lot of vacuum in
it (slab calculations, open zeolite systems, and so on), it is more efficient in this case to apply the
pseudopotential in real space. The computational cost of this method increases with the square of the
number of atoms and so is preferable for big systems. CASTEP uses the scheme developed originally for
norm-conserving potentials (King-Smith et al., 1991 ) and was subsequently generalized for the case of
ultrasoft pseudopotentials.
The separation of electrons into core and valence creates a problem when treating exchange-correlation
interactions. Within the core region of the nucleus the densities of the two subsystems overlap which
makes it difficult to cleanly descreen the pseudopotential during its generation. The only term in the
potential energy operator that is nonlinear with respect to the electron density is the exchange-
correlation energy. It has been shown by Louie et al. (1982) that there is a simple explicit scheme for
treating the nonlinear exchange and correlation interaction between the core and the valence charge
densities. This approach leads to significant improvements in the transferability of the potential. In
particular, the spin-polarized calculations become noticeably more accurate. The nonlinear core
correction (NLCC) term is especially important when semicore states are not explicitly treated as
valences. On the other hand, their explicit inclusion into the valence subsystem essentially removes the
need for the NLCC treatment.
Norm-conserving pseudopotentials
The main requirement of the pseudopotential approach is that it reproduces the valence charge density
associated with chemical bonds. It has been shown (Hamann et al., 1979) that for pseudo and all-
electron wavefunctions to be identical beyond the core radius, Rc, it is necessary for the integrals of
squared amplitudes of the two functions be the same. This is equivalent to requiring norm-conservation
from pseudo wavefunctions, that is, each should carry exactly one electron. This condition ensures that
the scattering properties of the pseudopotential are reproduced correctly.

Figure 1. Schematic representation of the all-electron and pseudized wavefunctions and potentials
The typical method for generating pseudopotentials is as follows. All-electron calculations are carried out
for an isolated atom in a chosen electronic configuration (not necessarily in the ground state). This
provides valence electron eigenvalues and valence electron wavefunctions for the atom (shown as ψ in
Figure 1). A parameterized form for the ionic pseudopotential (or the pseudo wavefunction) is chosen.
The parameters are then adjusted, so that a pseudoatom calculation with the same exchange-
correlation potential as in the all-electron atom gives pseudo wavefunctions, ψps (Figure 1), that match
the valence wavefunctions outside some cutoff radius, Rc, and pseudoeigenvalues that are equal to the
valence eigenvalues. This procedure involves direct inversion of the radial Kohn-Sham equation in the
case when the pseudo wavefunction and not the pseudopotential itself are parameterized. If each
wavefunction, pseudo and all-electron, is normalized to one, then the norm-conservation constraint is
automatically satisfied as a result of matching the wavefunctions outside Rc.
The ionic pseudopotentials are constructed with Rc ranging from one to two times the value of the
physical core radius. The smaller the value of Rc, the harder and more transferable the potential. The
conflicting effect of Rc creates an obvious trade-off between accuracy and efficiency.
Optimized pseudopotentials
A number of recipes exist for producing pseudopotentials that are optimized with respect to the energy
cutoff required in solid-state calculations.
Lin et al. (1993) suggested the following generation scheme based on the earlier work of Rappé et al.
(1990):

1. The pseudo wavefunction ψl(r) inside a cutoff radius is expressed as:

Eq. CASTEP 5
Where:
jl(qir) are spherical Bessel functions with (i-1) zeroes between r=0 and r=Rc. The cutoff radius
value is as large as possible, consistent with satisfactory transferability of the potential.
2. The coefficients αi are determined from minimizing the kinetic energy beyond the cutoff vector qc:
Eq. CASTEP 6
where qc is chosen to be equal to q4 from Eq. CASTEP 5. Three additional constraints that are
satisfied using Lagrange multipliers are the normalization of the pseudo wavefunction and the
continuity of the first two derivatives of the pseudo wavefunction at Rc.
3. The standard step of inverting the radial Kohn-Sham equation produces a smooth pseudopotential
with optimal convergence properties.
Lee (1996) suggested further enhancements and it is essentially this scheme that was used to generate
the bulk of norm-conserving pseudopotentials in the CASTEP database. This generation method
eliminates the condition that the second derivative of the pseudo wavefunction must be continuous at
a given cutoff radius because it automatically satisfies the second derivative constraint. As a result, the
scheme allows one to tune qc for a given Rc to optimize the accuracy and efficiency of a pseudopotential.
Ultrasoft pseudopotentials
Ultrasoft pseudopotentials (USP) were introduced by Vanderbilt (1990) in order to allow calculations to
be performed with the lowest possible cutoff energy for the plane-wave basis set. Since it is understood
that there are inherent limits on optimizing the convergence of norm-conserving pseudopotentials, a
completely different approach has been designed.
The rationale behind USP is that, in most cases, a high cutoff energy is only required for the plane-wave
basis set when there are tightly bound orbitals that have a substantial fraction of their weight inside the
core region of the atom. In these situations, the only way to reduce the basis set is to violate the norm-
conservation condition by removing the charge associated with these orbitals from the core region. The
pseudo wavefunctions are thus allowed to be as soft as possible within the core, yielding a dramatic
reduction in the cutoff energy.
Technically, this is accomplished by introducing a generalized orthonormality condition. In order to
recover the full electronic charge, the electron density given by the square moduli of the wavefunctions
is augmented in the core regions. The electron density can thus be subdivided into a soft part extending
through the unit cell and a hard part localized in the core regions.
USP formalism in solid state
The total energy in the USP scheme has the same form as other pseudopotential plane-wave methods,
with the nonlocal potential VNL given as:

Eq. CASTEP 7
where the projectors β and coefficients D(0) characterize the pseudopotential and differ for different
atomic species. The index I refers to an atomic site. The electron density in the expression for the total
energy is given by:
Eq. CASTEP 8
where ϕ are the wavefunctions and Q(r) are the augmentation functions that are strictly localized in the
core regions. The ultrasoft potential is fully determined by the local part, Vlocion(r) and by the
coefficients D(0), Q, and β. The algorithm that generates these quantities is described below.
The relaxation of the norm-conserving constraint is achieved by introducing a generalized
orthonormality condition:
Eq. CASTEP 9
where S is a Hermitian overlap operator:

Eq. CASTEP 10
where coefficients q are obtained by integrating Q(r). Kohn-Sham equations can be rewritten for the
USP case as:
Eq. CASTEP 11
where H can be presented as a sum of kinetic energy and local potential:

Eq. CASTEP 12
where Veff contains Vlocion(r), Hartree and exchange-correlation terms. All the terms arising from the
augmented part of the electron density are grouped with the nonlocal part of the pseudopotential (Eq.
CASTEP 7) by defining new coefficients:
Eq. CASTEP 13
The difference compared with the norm-conserving case is the presence of the overlap operator S, the
wave-function dependence of the coefficients D and the fact that the number of projector function β is
typically twice as large. A number of calculations related to augmentation charges can be carried out in

real space because of the localized nature of the function involved, so that the overall impact of these
extra steps on efficiency is not large.
Further technical details of the USP implementation, including expressions for the derivatives of the
total energy, can be found in Laasonen et al. (1993).
Pseudopotential generation
As in the norm-conserving case, an all-electron calculation is carried out on a free atom, leading to a
screened atomic potential, VAE(r). For each angular momentum a set of reference energies, εl, is
chosen. Typically two reference energies are sufficient. These energies should cover the range over
which good scattering properties are required. At each reference energy the solution of the radial Kohn-
Sham equation which is regular at the origin is obtained. Next cutoff radii Rcl are chosen and for each all-
electron wavefunction ψ generated above, a pseudo wavefunction ϕ is constructed. The only constraint
is that it should join smoothly to ψ at Rcl. A smooth local potential, Vloc(r), is generated to match VAE(r)
smoothly at a cutoff radius, Rloc. An auxiliary radius, R, is defined to be slightly higher than all of the core
radii. Finally, the local orbitals are formed (they vanish beyond R):
Eq. CASTEP 14
and their matrix of inner products:
It is now possible to define the quantities needed for the solid state calculation (Vlocion(r), D(0), Q, and
β):
Eq. CASTEP 15
Eq. CASTEP 16
and Vlocion(r), D(0) are produced using a descreening procedure:

Eq. CASTEP 17
Eq. CASTEP 18
Note: The non-linear core correction term can be introduced in the descreening procedure, Eq.
CASTEP 17, in exactly the same way as in the norm-conserving case.
Note: The formalism described above is based on the non-relativistic Schroedinger approach. With
CASTEP you can also use a scalar-relativistic approach either as a Koelling-Harmon (1977) scheme or as
its approximation commonly referred to as ZORA, zeroth order regular approximation (Lenthe et al.
1994).

The following conditions are satisfied in this scheme:

The pseudo eigenvalues are equal to the all-electron ones, and the corresponding orbitals match
exactly outside the core radii.
The scattering properties are correct at each reference energy. Thus, the transferability can be
systematically improved by increasing the number of such energies.
The valence charge density is precisely equal to the all-electron valence density in the reference
configuration.
Nonlinear core correction
The nonlinear core correction (NLCC) was first proposed by Louie et al. (1982) as a way of obtaining
accurate pseudopotential descriptions of magnetic systems. It has been shown, however, that NLCC is
equally important for spin non-polarized systems with semicore electrons.
The reason that the NLCC is required is found in the total energy expression in DFT:
Eq. CASTEP 19
In the pseudopotential formalism, the charge density is divided into core and valence contributions. The
energy of the core is assumed to be constant and is subtracted out. Thus, in Eq. CASTEP 19 above the
total charge density is replaced by a (pseudo) valence charge density and Eion is evaluated using
pseudopotentials.
As a result all interaction between core and valence electrons is transferred to the pseudopotential. This
implies linearization with respect to charge density which can only be an approximation to the kinetic
energy and the explicitly nonlinear exchange-correlation energy.
This linearization is obviously a good approximation when core and valence densities are well separated
in space. However, if there is significant overlap between the two densities, it will be the source of
systematic errors and will lead to reduced transferability of the potential.
The solution to the NLCC problem lies in a modifying the pseudopotential generation procedure and the
solid-state algorithm. In a typical generation scheme a screened atomic potential Vl is produced for each
angular momentum channel subject to certain constraints, for example norm-conservation, matching
eigenvalues to all-electron values, and so on.
These screened potentials give rise to atomic pseudowavefunctions that represent valence states only.
The valence pseudo charge density is constructed from these wavefunctions and is used to descreen the
potential to produce the bare ionic potential:
Eq. CASTEP 20
Since the exchange-correlation potential is a nonlinear function of the charge density, it can be shown
that this procedure, especially for spin-polarized systems, creates ionic pseudopotentials that are
dependent on the valence configuration. Louie et al. (1982) suggested substituting Eq. CASTEP 20 with
the following expression:
Eq. CASTEP 21
Here the total exchange-correlation potential is subtracted from the screened atomic potential. In
addition, the core charge must now be added to the valence charge whenever the exchange-correlation
potential is calculated. This additional atomic information has to be passed on to CASTEP and the core

charge is deemed to be the same in all applications. A drawback of this is that the core charge is difficult
to represent accurately on the Fourier grid used in pseudopotential calculations. Furthermore, the core
density is usually bigger than the valence density, so its presence might mask effects related to valence
charge density.
The next step in developing the formalism was to introduce the partial core correction. This approach
recognizes the fact that only the area of overlap between the core and valence densities is of interest.
Core density close to the nucleus is of no consequence although this is precisely the part of the core
density that causes the problems described above. Partial NLCC replaces the full core density with a
function that coincides with ρc outside a certain radius, and falls off smoothly toward the nucleus.
CASTEP uses a partial core correction with numerical core density in the case of ultrasoft
pseudopotentials for certain elements. The database of norm-conserving potentials does not, however,
include NLCC information.
Real-space representations of pseudopotentials
The nonlocality of the pseudopotential only extends over the region occupied by the core of the atom.
As the core region is relatively small, it should be possible to deal efficiently with the nonlocality of the
pseudopotential by working in real space. Only a small number of operations should be required to
project the angular momentum components of each wavefunction in the core of each atom.
Furthermore, the number of operations needed to project the angular momentum components of a
single wavefunction around a single atom in real space is independent of the size of the system, leading
to better scaling with system size than in the reciprocal space projection scheme. The computational
cost of the real-space implementation increases with the square of the number of atoms, compared
with the cubic relationship that exists for reciprocal space projection methods (Payne et al., 1992).
CASTEP uses the scheme developed originally for norm-conserving potentials (King-Smith et al., 1991)
and subsequently generalized for the case of ultrasoft pseudopotentials. The reciprocal-to-real space
transformation involves the following steps:
Select the plane wave cutoff, Gmax, which is to be used in the solid-state calculation.
Set χl(q) = Vl(q) for 0 < q < Gmax and χl(q) = 0 for q > γ, where γ is the difference between the ideal
Fourier grid size with no wrap-around errors for potential evaluation (at least 4Gmax). The Fourier
transform of the pseudopotential Vl(q), is defined as:
Eq. CASTEP 22
where Vl(r) is the original nonlocal projector and jl(qr) is the spherical Bessel function.
Select a real-space cutoff radius, R0. Generally this is about 1.5-2.0 × Rc, where Rc is the core radius
used in pseudopotential generation.
Variationally select χl(q) in the intermediate region, Gmax < q < γ by minimizing:
Eq. CASTEP 23
The object of this step is to achieve the best possible convergence of the modified potential in real
space.
Transform χl(q) back to real space to get χl(r ) which is now used in the real-space evaluation of
nonlocal potential matrix elements in solid-state calculations.

The modified real-space projectors are no longer identically zero outside Rc, although the minimization
in Eq. CASTEP 23 ensures the best possible convergence compatible with the removal of the wrap
around error. A quantitative measure of the error introduced by the transformation is given by:
Eq. CASTEP 24
This error function should be small (less than 0.001) for all wavevectors, q, and can be inspected in the
CASTEP output file.
One should bear in mind that the use of real-space scheme represents an approximation and that more
accurate results are obtained with the reciprocal-space version. The accuracy of the real-space
transformation is controlled by the value of the cutoff radius, R0. The default set of these values in
CASTEP is designed to be for accuracy rather than performance. It is advisable to carry out independent
tests on small systems before embarking on large-scale calculations with drastically reduced R0 values.
The real space transformation of the pseudopotential depends on the cutoff energy for plane wave basis
set, and thus it is not possible to precalculate real-space projectors in the same way as the reciprocal
space potentials (which are provided in CASTEP database).
Plane wave basis set

Bloch's theorem states that the electronic wavefunctions at each k-point can be expanded in terms of a
discrete plane-wave basis set. In principle, an infinite number of plane waves is required for such an
expansion. However, the coefficients, Ck + G, for the plane waves with small kinetic energies, |k + G|2,
are more important than those with large kinetic energies. Thus, the plane wave basis set can be
truncated to include only plane waves that have kinetic energies that are smaller than some particular
cutoff energy as illustrated in Figure 1 (the radius of the sphere is proportional to the square root of the
cutoff energy).
Figure 1. Schematic representation of the cutoff energy concept

Such that:

The truncation of the basis set at a finite cutoff energy will lead to an error in the computed total energy
and its derivatives. It is possible to reduce the magnitude of the error in a systematic way by increasing
the value of the cutoff energy. In principle, the cutoff energy should be increased until the calculated
total energy converges within the required tolerance. This would be the recommended procedure if, for
example, you were conducting a phase stability study where the absolute values of total energies of
different structures are compared. However, the energy differences for the same structure converge at
much lower cutoff energies than the total energy itself. This is due to the cancellation of errors and
allows one to use moderate basis sets for reliable geometry optimization or molecular dynamics studies.
These arguments are also valid for the convergence testing of Brillouin zone sampling.
Finite basis set correction
One of the difficulties associated with the use of plane-wave basis sets is that the number of basis states
changes discontinuously with cutoff energy. In general these discontinuities will occur at different
cutoffs for different k-points in the k-point set. In addition, at a fixed cutoff energy, a change in the size
or shape of the unit cell will cause discontinuities in the plane wave basis set. This problem can be
reduced by using a denser k-point set, so that the weight attached to any particular plane wave basis
state is reduced. However, the problem is still present even with quite dense k-point samplings. It can be
handled approximately by applying a correction factor that accounts for the difference between the
number of a states in a basis set with an infinitely large number of k-points and the number of basis
states actually used in the calculation (Francis and Payne, 1990).
The finite basis set correction is of the utmost importance when cell optimization is performed with a
basis set that is not absolutely converged. For example, the norm-conserving silicon pseudopotential is
sufficiently soft and provides accurate results with a cutoff energy for plane waves of about 200 eV.
However, if one calculates the equation of state using this cutoff (that is, the volume dependence of the
total energy and pressure), the volume that corresponds to the minimum in total energy does not
coincide with the volume that gives zero pressure. As one repeats such EOS calculations at progressively
higher cutoff energies and with better k-point sampling, the difference between the two volume values
becomes smaller and smaller. In addition, the E-V curve calculated at low cutoff energy is jagged but
becomes more and more smooth as the cutoff energy is increased. The reason for the jagged
appearance of the E-V curve is the discontinuous change in the number of plane waves used at the same
cutoff energy but for different lattice constants. The finite basis set correction, when added to the total
energy, allows one to perform calculations with a fixed number of basis states and to interpolate the
results as if the more physical condition of a fixed energy cutoff were used. A detailed description of the
recommended use of this technique can be found in Milman et al. (1994).
The only parameter that must be known in order for this correction term to be evaluated is dEtot/d
lnEcut, where Etot is the total energy of the system and Ecut is the cutoff energy. CASTEP can calculate
this term automatically or you can input this parameter manually.
The value of the dEtot/d lnEcut gives a good indication of the convergence of the calculation with respect
to the energy cutoff and k-point sampling. When its value per atom (that is, the value reported in the
CASTEP output file divided by the number of atoms) is smaller than 0.01 eV/atom, the calculation can be
considered very well converged. A value of 0.1 eV/atom is sufficient for most calculations.
Self-consistent electronic minimization

CASTEP offers a choice of methods for electronic relaxation. The default method is the most efficient and
is based on density mixing (Kresse and Furthmuller, 1996). In this scheme, the sum of electronic
eigenvalues is minimized in the fixed potential instead of the self-consistent minimization of the total
energy. The new charge density at the end of the minimization is mixed with the initial density and the
process is repeated until convergence is reached. A number of options are supported for this scheme:
linear mixing, Kerker mixing, Broyden mixing, and Pulay mixing, in order of increasing robustness. The

conjugate gradient-based approach is used to minimize the sum of eigenvalues. A slightly more
elaborate scheme that involves separate mixing of spin density has been developed for spin-polarized
calculations.
CASTEP also supports a more traditional scheme for electronic relaxation, involving minimization of the
total energy. The electronic wavefunctions are expanded using a plane-wave basis set and the expansion
coefficients are varied so as to minimize the total energy. This minimization is performed by using an all-
bands method that allows simultaneous update of all wavefunctions. The scheme uses a preconditioned
conjugate gradients technique (Payne et al., 1992).
The main advantage of the density mixing method is its robustness for metallic systems, especially for
metallic surfaces. A traditional total energy minimization scheme might become unstable in a metallic
system with the cell elongated in one dimension, which is the typical setup for supercell calculations on
surfaces. The density mixing scheme converges equally well for insulating and metallic cases, and offers
at least a factor of three increase in speed for moderately sized insulator systems.
Note: When using the density mixing method, the SCF energy no longer decreases monotonically to
the final converged SCF energy and unconverged energies may have values lower than the final
converged energy. This behavior is due to the fact that in the density mixing method, the Harris
functional for the energy is used, rather than the Kohn-Sham functional. Unlike the Kohn-Sham
functional, the Harris functional does not necessarily have a minimum at the SCF solution.
Preconditioning
All electronic relaxation methods in CASTEP use preconditioning to speed up the rate of convergence
(Payne et al., 1992). The idea is to find a matrix which, when multiplied with the residual vector, gives the
exact error in the wavefunction. Formally, this matrix can be written down as:
Eq. CASTEP 28
where εn is the exact eigenvalue for the band being optimized. It in not possible to evaluate this matrix,
but by recognizing that the kinetic energy dominates the Hamiltonian for large G-vectors, it is possible to
approximate the matrix by a diagonal function which converges to G-2 for large G-vectors and is
constant for small G-vectors. The actual form of the matrix is (Payne et al., 1992):
Eq. CASTEP 29
where x is the ratio of |k + G|2 to the kinetic energy of the given state.
Application of the preconditioning scheme causes all of the large wave-vector components of a
wavefunction to converge at nearly the same rate.
Density mixing schemes
CASTEP supports four schemes for generating new starting charge densities from the results of the
previous SCF step (Kresse and Furthmuller, 1996). The simplest is the linear mixing scheme. This method
requires one parameter and the output density is produced as a linear combination of the input and
output densities on the last iteration.
Kerker mixing recognizes the fact that small-G components of the charge density should be mixed with
smaller weights in order to prevent charge sloshing during SCF optimization. The new density is given
by:

Eq. CASTEP 30
The Kerker scheme is, consequently, defined by two parameters, the mixing amplitude, A, and the
cutoff wavevector, Gmax.
The most efficient mixing scheme is Pulay's scheme. In this approach, the input charge density and the
residual vectors are stored over a number of SCF optimization steps. A new input density is obtained in
each step as a linear combination of charge densities of all previous steps. The new density is
determined such that it minimizes the normal of the residual vector subject to the constraint of
conserving the number of electrons. Pulay's scheme starts with a Kerker-type step, so it is effectively
controlled by three parameters: the mixing amplitude, A, the cutoff wavevector, Gmax, and the depth of
the optimization history.
Broyden mixing is very similar to the Pulay scheme, except that it performs a quasi-Newton relaxation
instead of DIIS minimization of the residuals.
Treatment of metallic systems
The main difference between metals and insulators, from the technical point of view, is that the number
of occupied bands is not the same at different k-points in the Brillouin zone. The number of occupied
bands for insulators is calculated as one half the total number of valence electrons, but this approach is
not suitable for metals. Partial occupancies are introduced to eliminate discontinuous changes in total
energy that are created when an energy band crosses a Fermi level during SCF minimization.
The overall strategy for treating metallic systems in CASTEP is as follows. The number of bands has to be
slightly higher than would be required for an insulator. It may be necessary to add more bands if
convergence is slow, especially for spin-polarized systems. An artificial electronic temperature is then
introduced by assuming Gaussian-like smearing of each energy level (de Vita, 1992). Occupation
numbers are deduced from the ratio of the area of the Gaussian that falls below the Fermi level to its
total area. Thus, a level deep in the valence band has an occupation number of 1, a level directly on the
Fermi surface has an occupation number of 0.5, and a level high above the Fermi energy is empty. In
some sense, this is the same as giving the Kohn-Sham particles a finite temperature. Therefore, CASTEP
uses the Mermin finite temperature expression for the total energy (Marzari, 1997):
E = EKS - TS
where:
T is the temperature (that is, smearing width)
S is the Mermin entropy due to the different ways in which the partially filled bands could have been
filled
The CASTEP output is as follows. The line
Final energy, E = -861.8315373731 eV
gives the Kohn-Sham energy, EKS, which ignores the entropy. However, it is the total Mermin free
energy that is minimized by CASTEP and reported in the SCF cycles in the line
Final free energy (E-TS) = -861.8315374521 eV
If you were actually interested in the electronic states at some reasonable nonzero temperature, you
would smear the Fermi level with a thermal (that is, Fermi-Dirac) smearing method and the free energy
reported by CASTEP would be the value you require.
Note: Temperature equivalent of energy is given by the conversion factor of 11604.5 K/eV; so the
default smearing width of 0.1 eV corresponds to a very high temperature of 1160 K.

However, it is often the T = 0 K value that is required and the smearing is necessary to improve the
convergence of the numerical algorithm. As the smearing ('temperature') is increased, the TS term
increases and the free energy, EKS - TS, goes down. At the same time, as the entropy contributes more
and more to the free energy, the electronic minimization pays less attention to theEKS term, so the final
EKS increases. Because the dependence of the free energy and the Kohn-Sham energy on the smearing
width is the same (to first order), averaging the two values gives a much better approximation to the T =
0 K result:
NB est. 0K energy (E-0.5TS) = -861.8315374126 eV
The total energy calculated by CASTEP for metals is thereby corrected for the fact that it now includes
the artificial electronic entropy contribution. This correction is possible because a closed analytical form
for the dependence of the total energy on the smearing width (or electronic temperature), s, exists. In
principle, evaluation of Etot (s -> 0) is necessary in order to obtain a physically meaningful energy. In the
past, values for s as low as 0.01 eV have been used to calculate the converged energy. The total energy
correction described above allows the use of a much higher smearing width (up to 1 eV), while still giving
results converged with respect to s. The advantage is the added stability of the calculation, since
occasional Fermi-level crossings do not create instabilities. However, there is no simple expression for a
similar correction for either atomic forces or stress on the unit cell.
The error in the forces introduced by this limitation is generally small and acceptable. Nonetheless,
geometry optimizations for metals should be performed with some caution. You should use smaller
smearing values than for single-point energy runs. The calculated forces will be more accurate, but there
is a risk of instability, since changes in atomic geometry are likely to cause reordering of bands and some
Fermi-level crossings. Cell optimization is also more difficult for metallic systems, since the stress tensor
could be affected by nonphysical contributions from nearly empty conduction bands.
Disorder in solids
Many crystal structures possess static positional disorder. The crystal may either contain fewer atomic
species than there are crystallographically equivalent sites to populate, or there might, for example, be
statistical occupancy of a given crystallographic site by more than one type of atom in different unit
cells. This positional disorder is typically manifested in site occupancy factors of less than unity for the
average unit cell.
Materials Studio allows you to model positional disorder by specifying atom occupancy and by defining
mixture atoms.
Atom occupancy
The vast majority of atoms will have an occupancy of unity. However, in the case of an atom on a
partially occupied interstitial position, you can specify an occupancy ranging from 0.0 to 1.0.
Atom occupancies can be modified in the Properties Explorer.
Mixture atoms
Atomic sites in a crystal can also be described in terms of a hybrid atom that consists of two or more
element types. The relative concentrations can be set for any number of atoms, but the total
concentration must not exceed 100%. The mixture atoms description is the most often used
representation of solid solutions, metallic alloys, disordered minerals, and so on.
Disorder and first principles calculations

There are a number of different approaches for dealing with disorder in first principles calculations:

Virtual crystal approximation (VCA): this offers technically the simplest approach, allowing
calculations on disordered systems to be carried out at the same cost as calculations for ordered
structures. VCA ignores any possible short range order and assumes that on each potentially
disordered site there is a virtual atom which interpolates between the behavior of the actual
components. This approach neglects such effects as local distortions around atoms and cannot be
expected to reproduce the finer details of the disordered structures very accurately.
Using large ordered supercells followed by configurational averaging: this is a very expensive
approach with limited applicability. For example, it is not possible to treat arbitrary and particularly
small concentrations.
Coherent potential approximation (CPA): this method approximates a configurationally random alloy
with an effective medium that is determined self-consistently from the condition of stationary
scattering. The CPA technique is used extensively with model Hamiltonians with well-known
scattering properties or in the context of multiple scattering methods of band structure calculation
(KKR, LMTO). CPA is not well suited to total energy calculations or geometry optimization tasks.
"Computational alchemy": this method uses the perturbation theory to calculate the response to
the difference between the true and VCA potentials. This approach is very demanding
computationally, as are all linear response calculations.
The basic ideas of the workable VCA implementation for DFT methods, in particular for the
pseudopotential-based techniques, were set out by Bellaiche and Vanderbilt (2000). The main statement
for the implementation of VCA with ultrasoft potentials can be expressed as:
Eq. CASTEP 86
where the total external potential is generated as the sum of the nonlocal potentials of each atomic
species, α, taken with the weights, w, of the component atoms in the mixture atom. This means that all
the key components of the ultrasoft potentials, that is, the local part, Vloc, and the D and Q matrices,
are all weighted according to the site occupancies.
The VCA scheme described above has been applied successfully to study disorder in the perovskites Pb
(ZrTi)O3 (Bellaiche and Vanderbilt, 2000) and BiScO3-PbTiO3 (Iniguez et al., 2000), and Al-Si disorder in
silicates such as hollandite and gehlenite (Winkler et al., 2002).
Note: Ramer and Rappé (2000) suggested an alternative scheme where the pseudopotentials are
generated on the fly for the mixture atoms. Their scheme appears to be less readily generalized for
the case of more than two disordered species or where the mixture atom's components have
different chemical valences.
Limitations of VCA implementation in CASTEP

The VCA approach is not intended as a universal method for conducting studies of disordered materials.
It often produces useful results, but it is important to be aware of its limitations.
Theoretical limitations
VCA is not expected to be better than 50% accurate for excess properties of solid solutions, even for the
applications that use simple forcefields. The deviation from the Vegard law, for example, can only be
reproduced qualitatively for many systems. In fact, CASTEP calculations for NaCl/KCl mixtures with
norm-conserving potentials fail to describe even the shape of the excess volume curve (the difference
between the calculated volume at a given concentration and the linear combination of the volumes of
the end-members). It should be noted that the excess properties are very sensitive to the accuracy of

the data for the end-members and, in general, this is not the preferred application of VCA in CASTEP. On
the other hand, properties such as the bulk modulus of the NaCl/KCl solid solution are described very
well within the same framework (see Figure 1).
An important aspect of the VCA implementation has not been discussed by the authors of the formalism
(Bellaiche and Vanderbilt, 2000). One should always test the pseudopotentials for the presence of ghost
states. They often manifest themselves in the solid state calculations as a strong change in the total
energy as a function of the energy cutoff of the plane wave basis set. It seems that the ultrasoft
potentials are prone to generating ghost states in the VCA framework, while none of the individual
potentials has a ghost state. The NaCl/KCl system could not be studied with the ultrasoft potentials for
this very reason - the finite basis set correction calculated for solid solutions was orders of magnitude
higher than for the end-members. This is a clear indication of a ghost state in the calculation. There is no
easy way of testing the VCA approach for ghost states, so one should always examine the value of the
derivative of the total energy as displayed in the output file during the finite basis set correction
calculation. It should be of the same order as the derivatives for the end-member structures.
Technical limitations
Atom occupancy cannot be used with the current CASTEP implementation of the virtual crystal
approximation (VCA). Partial atom occupancy can be considered as a special case of a mixture atom,
where one part of the mixture is an atom of "nothing". This case is not supported for a number of
technical and fundamental reasons.
Current implementation of the molecular dynamics algorithms in CASTEP is not yet compatible with the
VCA formalism. None of the MD schemes (NVE, NPT, and so on) works for disordered crystals in the
current version.
Linear response calculations (phonons, polarizability) are not supported for disordered crystals.
Test results
The VCA implementation in CASTEP is capable of correctly describing a number of mixture atoms, as
shown by the results below.
Bulk modulus of NaCl/KCl solid solution
The bulk modulus of the halite-sylvite mixture (NaCl/KCl) has been calculated as a function of
concentration by calculating the P-V equation of state for different Na concentration and fitting them
with the third-order Birch-Murnaghan analytical expression. The results agree with the experimental
data (Figure 1) to better accuracy than is typically achieved for the ordered crystals. The norm-
conserving pseudopotentials were used in this study (all other tests described below were carried out
with ultrasoft pseudopotentials).

Figure 1. Dependence of the bulk modulus of the NaCl/KCl solid solution on concentration.
Experimental data are from Walker et al. (2004). The solid line shows a polynomial fit to the calculated results.
The structure of bicchulite

The structure of the cubic mineral bicchulite, Ca2[Al2SiO6](OH)2, was calculated and compared to the
experimental results (Sahl, 1980). Each Si/Al site is completely disordered in this structure, so the weights
are 2/3 and 1/3 for Al and Si atoms, respectively. The lattice parameter is calculated as 8.675 Å, or 1.7%
lower than the experimental value. The interatomic distances calculated for the structure are (Si,Al)-O =
1.6968 Å (-1.1%) and Ca-O = 2.3009 Å (-0.4%) and 2.3794 Å (-3.2%). This level of accuracy in the structural
description is acceptable for a DFT calculation.
The structure and stability of Pb(Zr,Ti)O3 perovskites
The structures and energies of three different modifications of the 1:1 PZTO ceramics were calculated
and the results compared with the experimental data and the earlier VCA results (Ramer and Rappé,
2000). The modifications studied include tetragonal P4mm and rhombohedral R3m and R3c phases. The
results are summarized in the tables below.
Table 1. Structure of the P4mm tetragonal phase of PZTO. Experimental data are from Frantti et al.
(2000), earlier VCA results are from Ramer and Rappé (2000).
a (Å) c (Å) c/a Tiz O1z O2z Pb-O2 (Å) Ti-O1 (Å) Ti-O2 (Å)
CASTEP 4.0481 4.1283 1.020 0.5573 0.6112 0.0926 2.600 1.918 2.036
exp. 4.0303 4.1449 1.028 0.5649 0.6110 0.0921 2.508 1.960 2.024
VCA 3.9760 4.1050 1.033 - - - - - -

Table 2. Structure of the R3m rhombohedral phase of PZTO. Experimental data are from Amin et al.
(1981), earlier VCA results are from Ramer and Rappé (2000).
a (Å) α (°) Ox Oy Pbx Tix Pb-O (Å) Ti-O (Å)
CASTEP 4.0749 89.535 -0.0040 0.5080 0.5586 0.0250 2.516 1.973, 2.115
exp. 4.0809 89.676 -0.0046 0.5092 0.5620 0.0216 2.537 1.994, 2.098
VCA 4.0215 90 (fixed) - - - - - -
Table 3. Structure of the R3c rhombohedral phase of PZTO. Experimental data are from Jirak and
Kala (1988), earlier VCA results are from Ramer and Rappé (2000).
a (Å) α (°) Ox Oy Oz Pbx Tix Pb-O (Å) Ti-O (Å)
CASTEP 5.7726 59.589 0.4942 0.0284 -0.0180 0.0283 0.2632 2.565 1.979, 2.111
exp. 5.8240 59.600 0.4860 0.0330 -0.0190 0.0341 0.2620 2.487 2.024, 2.109
VCA 5.6790 60 (fixed) - - - - - - -
Table 4. Energy differences between the three phases of PZTO, in meV per 5 atom cell. Earlier VCA
results are from Ramer and Rappé (2000).
E(R3m) - E(P4mm) E(R3c) - E(P4mm)
CASTEP -4.7 -6.3
VCA 9 6
These results indicate that the structural features are reproduced quite accurately within VCA. Note that
the experimental data for rhombohedral phases are for Zr concentrations slightly different from 0.5,
since these phases are not stable for the 1:1 composition. The energy differences between the phases
are extremely small in recent studies and earlier work by Ramer and Rappé (2000). DFT energies cannot
be trusted at this level of accuracy to judge the relative stability of the polymorphs. For example, the
fact that the angles were fixed to 90 and 60° in the earlier VCA work suggests that after the full
optimization, the rhombohedral phases are likely to become more stable than the tetrahedral phase, in
agreement with the CASTEP results (Table 4).
The structure of leucite
Tetragonal leucite, KAlSi2O6, contains three different sites with a fully disordered distribution of Al and Si
cations. The structure is only slightly distorted with respect to the cubic cell and the accuracy of
reproduction of this distortion is a measure of the quality of the VCA description. The results presented
below (Table 5) show exceptionally good agreement with the experimental data. Furthermore, atomic
positions are also predicted very accurately. The highest deviation from the experimental data for any
individual fractional coordinate is 0.001 in the CASTEP calculations, compared with maximum deviations
of up to 0.007 in the forcefield modeling.

Table 5. Lattice parameters of leucite compared to experimental data (Mazzi et al., 1976 ) and the
results of forcefield calculations (Winkler et al., 1991).
a (Å) c (Å) c/a
CASTEP 13.1497 13.8318 1.052
exp. 13.09 13.75 1.050
empirical 12.9884 13.8000 1.062
CASTEP supports two schemes for geometry optimization: BFGS and damped molecular dynamics.
BFGS geometry optimization

The main advantage of the BFGS minimizer (Pfrommer et al., 1997) is the ability to perform cell
optimization, including optimization at fixed external stress. The BFGS scheme uses a starting Hessian
which is recursively updated during optimization. The CASTEP implementation involves a Hessian in the
mixed space of internal and cell degrees of freedom, so that both lattice parameters and atomic
coordinates can be optimized.
The LBFGS algorithm (low-memory BFGS) is expected to perform better for large systems. This approach
uses only a limited number of inverse Hessian updates to construct a new Hessian; this scheme has
been shown to scale linearly in memory, while BFGS scales as a square of the system size (Aarons, 2011).
The LBFGS algorithm also implements a universal sparse preconditioner that accelerates geometry
optimization by a factor of two for small systems and a factor of ten for very large ones (Packwood et al.,
2016).
When cell optimization is required, use of a finite basis set correction term is recommended. Calculating
the term is not too costly (10-30% of the self-consistent electronic minimization at the first iteration)
relative to the advantages that it provides. Cell optimization runs may be problematic if the finite basis
set correction is not used or if the energy cutoff is so low that the correction is not accurate. In these
circumstances, the optimization run may stop with a message which states that the energy has
converged, but that the stress is still non-zero. The minimizer attempts to find the energy minimum
rather than the stress zero-point, since the former is more meaningful under the circumstances.
Another potential pitfall is the use of the Fixed Basis Size Cell optimization setting when the starting
geometry is very different from the final one. The finite basis set correction depends on the cell size and
shape, although this dependence is disregarded by the minimizer. In addition, the effective cutoff
energy changes when the cell geometry is modified with the above setting (it is the number of plane
waves that is kept fixed). If this change takes the dEtot/d(ln Ecut) function far away from the point that
was used to evaluate the finite basis set correction, the results will not be accurate. Therefore, you
should compare the starting and final geometries and perform a completely new run starting from the
final configuration if the difference between the two structures is large.
Constraints
CASTEP can perform geometry optimization with constraints applied. The simplest type of constraint is
to fix the atom positions. In CASTEP, this means fixing the fractional coordinates of the atoms.
Note: Atoms on special positions need not be fixed manually as the symmetry treatment in CASTEP
ensures the correct behavior of such atoms.

It is also possible to fix lattice parameters. Once again, it is only necessary to do this for parameters that
are not fixed by symmetry. This type of constraint is often useful in phase stability studies when, for
example, you want to fix the angles to 90° (Winkler and Milman, 1997).
It is also possible to impose more general linear constraints on atomic coordinates. These constraints
are specified using a matrix that transforms the Cartesian coordinates of all atoms to the subspace of
unconstrained coordinates. This facility is intended for fixing, for example, the z-coordinates of atoms in
slab calculations of surface processes.
Non-linear constraints
Non-linear constraints refer to constraints on interatomic distances (bonds), angles, and torsions. Such
constraints can be imposed using the delocalized internals optimizer.
Estimated compressibility
You can facilitate cell optimization convergence by making a reasonable initial estimate of the bulk
modulus for the material. The initial changes to lattice vectors are calculated on the basis of this value
(and, of course, based on the calculated stress tensor). When the estimated bulk modulus is too high,
the steps become smaller than is ideal for the minimizer; therefore, it is conceivably possible that you
could reduce the number of geometry optimization steps by reducing this value. On the other hand, too
small a bulk modulus for a hard material could result in an oscillating behavior, where the first step is too
big. Thus, prior knowledge of the hardness of the material could help to reduce the number of steps
required for calculations. The effect of a judicious choice of the initial bulk modulus value is illustrated in
the table below (times are given relative to that of the calculation using an initial value of 500 GPa).
Compound Estimated bulk modulus (GPa) Number of steps Relative time

Cubane 5.000 15 0.98
50.00 15 0.87
250.0 15 0.82
500.0 20 1.00
1000.0 24 1.29
Glycine 5.000 46 1.29
50.00 42 1.03
250.0 39 0.92
500.0 37 1.00
1000.0 54 1.24
YBa2Cu3O7 5.000 12 0.81
50.00 13 0.74
250.0 12 0.81
500.0 17 1.00
1000.0 13 0.81

TPSD geometry optimization

The BFGS algorithm as implemented in CASTEP uses the assumption that the potential is quadratic to
determine an optimal step length per iteration. When this is not the case the BFGS algorithm does not
perform well and may take a long time to optimize the structure. A more robust Barzilai-Borwein (1988)
Two-Point Steepest Descent (TPSD) algorithm allows a larger range of problems to be solved. It is
specifically more efficient when cell optimization with user-supplied constraints is requested. This
scenario describes, for example, optimization of solid-solid interfaces strained to a substrate: that is, the
lateral cell parameters and all cell angles are fixed, only the cell dimension in the direction normal to the
interface is allowed to relax.
The TPSD algorithm requires only the gradient and position of the system at the current and previous
iteration, meaning that a relatively small amount of memory is consumed. From the difference of each
value between the iterations, a step size is calculated for use in the direction of the most negative
gradient from the current iteration. TPSD optimization has been found to converge reliably in a number
of situations where the BFGS algorithm takes too long to converge.
Damped molecular dynamics

Damped molecular dynamics presents an alternative method for geometry minimization that involves
only internal coordinates (the cell parameters have to be fixed). The method uses the critical damping
regime as a way of dealing with the ground state. The regime can be implemented either by using one
damping coefficient for all degrees of freedom (coupled modes) or by using different coefficients for
different degrees of freedom (independent modes). The latter approach allows you to freeze all modes,
both fast and slow, simultaneously. Alternatively, you can perform steepest descents damping with a
fixed coefficient. However, this is a less efficient approach. Indeed, it is not, strictly speaking, a molecular
dynamics technique, since it solves first-order equations of motion and not second-order equations.
Both independent modes and coupled modes damped molecular dynamics runs can be performed with
a bigger time step than undamped molecular dynamics simulations. When the system gets close to
equilibrium, the time step can be increased even further, since the fast modes freeze out before the slow
ones. CASTEP can automatically adjust the time step, leading to increased efficiency of the algorithm. It
is also recommended that you recalculate the damping coefficients periodically during a damped
molecular dynamics run. A full description of the method implemented in CASTEP can be found
elsewhere (Probert, 2003).
Dynamics
Molecular dynamics (MD) involves the stepwise integration of Newton's equations from a given starting
point. It is the most natural method of performing equilibrium statistical-mechanical calculations using a
simulation. Additionally, MD may be used to explore conformations, such as molecular adsorption sites
on a surface. If frictional forces are added to the equations of motion, Langevin dynamics becomes
possible, as does geometry optimization using damped MD. Finally, extended Lagrangian methods
allow thermostatic control of the temperature.
Molecular dynamics in total-energy DFT schemes is implemented in essentially the same way as in
conventional forcefield based methods. The main difference is that the energy and atomic forces are
derived by solving DFT equations rather than from empirical potentials of interatomic interactions.
Electrons are kept on the Born-Oppenheimer surface by means of explicit electronic structure
optimization after each MD step. A side effect of this is that evaluation of force and energy from first
principles is always the most computationally expensive part of ab initio MD. As a result, the efficiency of
the MD step itself has no impact on the speed of the calculation.

MD in CASTEP is based on the velocity Verlet algorithm for integration of the equation of motion. The
default time step can be as high as 1 fs with this algorithm because of its numerical stability and the
conservation of the constant of motion.
The efficiency of the method is due in large part to the introduction of wavefunction extrapolation
between MD steps (Arias et al., 1992). In addition, charge density extrapolation (Alfe, 1999) has been
introduced.
Wavefunctions and density extrapolation

The main idea behind the interpolation schemes is to provide a good starting model of the electronic
structure for the SCF optimization, after the geometry change. This can be achieved by using the multi-
linear extrapolation as proposed by Arias et al. (1992).
The problem with wavefunction interpolation is that wavefunctions may be multiplied by an arbitrary
phase factor or ordered in different ways in two contiguous steps. So, before the extrapolation is
performed, the two subspaces {ψn,k (t)} and {ψn,k (t-dt)} are aligned so that Σn,k |ψn,k (t)-ψn,k (t-dt)| is
minimized.
Then the wavefunctions at the next time step, t+dt, can be written as:
Eq. CASTEP 31
and similarly for the charge density:

Eq. CASTEP 32
The coefficients α and β are calculated by determining the best quadratic extrapolation of the atomic
positions. This extrapolation scheme not only speeds up the calculation but also improves conservation
of the constant of motion and dramatically reduces the "electronic drag" effect (Payne et al., 1992).
An improvement suggested by Alfe (1999) recognizes the fact that the charge density is mostly
determined by the superposition of the atomic charge densities. Therefore one can write:
Eq. CASTEP 33
where ρ(t) is the self-consistent charge density at time t, and ρat(t) is the sum of the atomic charge
densities. The charge at time t+dt is simply extrapolated as:
Eq. CASTEP 34
where the change of δρ is given by:

Eq. CASTEP 35
The atomic charge density can be calculated exactly and cheaply using the same methods as for
Mulliken population analysis. The resultant scheme includes extrapolation of wavefunctions using Eq.
CASTEP 31, extrapolation of charge density difference using Eq. CASTEP 35 and recalculation of the
atomic charge densities.
Experience shows that the second-order extrapolation scheme described above is not necessarily the
best or the fastest algorithm. CASTEP therefore offers a selection of extrapolation schemes that differ in
the way the coefficients are selected: 1st order extrapolation with variable coefficients; 2nd order

extrapolation with variable coefficients; alternating first and second order extrapolation steps with
variable coefficients; and similar combinations of 1st and 2nd order schemes with fixed coefficients. The
actual setting is controlled by the values of the and MD_EXTRAP_FIT keywords in the .param file. The
fixed coefficient scheme is based essentially on a Taylor expansion, while the variable coefficients
schemes are based on the best fit between extrapolated and MD-predicted atomic coordinates. It has
been shown that the accuracy of wavefunction extrapolation improves greatly when the coefficients are
chosen based on the extrapolation of atomic coordinates.
An alternative to using wavefunction extrapolation is to use extended Lagrangian formulation, XL-BOMD
(Steneteg 2010, Niklasson 2011) . The XL-BOMD scheme allows simultaneous propagation of nuclear and
electronic degrees of freedom and shows good energy conservation at time steps that are unusually
high for first principles calculations.
Ensembles
Integrating Newton's equations of motion allows you to explore the constant-energy surface of a
system. However, most natural phenomena occur under conditions where the system is exposed to
external pressure and/or exchanges heat with the environment. Under these conditions, the total
energy of the system is no longer conserved and extended forms of molecular dynamics are required.
Several methods are available for controlling temperature and pressure. Depending on which state
variables (the energy E, enthalpy H (that is, E +PV), number of particles N, pressure P, stress S,
temperature T, and volume V) are kept fixed, different statistical ensembles can be generated. A variety
of structural, energetic, and dynamic properties can then be calculated from the averages or the
fluctuations of these quantities over the ensemble generated.
Both isothermal (where heat is exchanged with a temperature bath to maintain a constant
thermodynamic temperature) and adiabatic (where no heat exchange occurs) ensembles are available:
Table 1. Thermodynamic ensembles handled by CASTEP
Ensemble
Constant temperature, constant pressure (NPT)
Constant energy, constant volume (NVE)
Constant pressure, constant enthalpy (NPH)
Constant temperature, constant volume (NVT)
NVE ensemble
The constant-energy, constant-volume ensemble (NVE), also known as the microcanonical ensemble, is
obtained by solving the standard Newton equation without any temperature and pressure control.
Energy is conserved when this (adiabatic) ensemble is generated. However, because of rounding and
truncation errors during the integration process, there is always a slight fluctuation, or drift in energy.
True constant-energy conditions (that is, without temperature control) are not recommended for the
equilibration phase of the simulation because, without the energy flow facilitated by temperature
control, the desired temperature cannot be achieved.
However, during the data collection phase, if you are interested in exploring the constant-energy surface
of the conformational space, or if for some other reason you do not want the perturbation introduced
by temperature- and pressure-bath coupling, this is a useful ensemble.

Nosé NVT dynamics

The Nosé thermostat (Nosé, 1984) generates deterministic dynamics, with the temperature controlled
by a fictitious additional coordinate, s, added to the Lagrangian of the system. The thermostat employs
a feedback loop between the instantaneous kinetic energy and the required temperature. The rate of
feedback is determined by the mass parameter, Q. This parameter should be chosen so that the natural
oscillation frequency of the Nosé coordinate is close to the characteristic frequency of the actual system.
The mass parameter is related to the thermostat relaxation time by:
Eq. CASTEP 36
Where:
g is the number of degrees of freedom (usually 3N - 3, where N is the number of atoms)
k B is the Boltzmann constant
T is the thermostat temperature
τ is the relaxation time.
An improvement on the standard Nosé thermostat (or Nosé-Hoover thermostat) is the Nosé-Hoover
chain method, described in detail by Tuckerman et al. (2001). In this method the kinetic energy
fluctuations of the thermostat variable are controlled by coupling it to another thermostat variable. The
kinetic energy fluctuations of the second thermostat are, in turn, controlled by coupling to a third
thermostat, and so on, to form a chain of M thermostats. This new coupling (the Nosé-Hoover "chain"
thermostatting mechanism) leads to a more general canonical dynamics method.
Langevin NVT dynamics
The Langevin thermostat generates stochastic dynamics using a Brownian motion model, implemented
using the fluctuation-dissipation theorem. It is controlled by the damping time parameter, which
controls the rate of decay of fluctuations in the temperature. In practice, this should be chosen such
that it is larger than the time scale of any motions of interest. An advantage of the Langevin description
is that it can be proved to provide ergodic results. The Nosé thermostat, on the other hand, provides
good short term dynamics, but fails to give ergodicity.
Nosé-Hoover-Langevin thermostat
The Nosé-Hoover-Langevin (NHL) thermostat suggested by Leimkuhler et al. (2009) combines the
advantages of the Nosé-Hoover chain method with the ergodicity of Langevin dynamics. In practical
terms this thermostat converges to equilibrium faster than the Nosé-Hoover chain method and offers
much better conservation of the constant of motion.
NPT ensemble
The constant-temperature, constant-pressure ensemble (NPT) allows control over both the temperature
and pressure. The unit cell vectors are allowed to change, and the pressure is adjusted by adjusting the
volume of the unit cell.
Pressure is currently controlled in CASTEP using either the Andersen or Parrinello-Rahman method.
Note: Only the size, and not the shape, of the unit cell can be changed with the Andersen method.
Temperature can be controlled using either the Nosé or the Langevin thermostat.
NPT is the ensemble of choice when the correct pressure, volume, and densities are important in the
simulation. This ensemble can also be used during equilibration to achieve the desired temperature and

pressure, before changing to the constant-volume or constant-energy ensemble when data collection
starts.
Andersen method of pressure control
In the Andersen (1980) method of pressure control, the volume of the cell can change, but its shape is
preserved by only allowing the cell to change isotropically.
The Andersen method is useful for liquid simulations since the box could become quite elongated in the
absence of restoring forces if the shape of the cell were allowed to change. A constant shape also makes
the dynamics analysis easier.
However, this method is not very useful for studying materials under anisotropic stress or undergoing
phase transitions, which involve changes in both cell lengths and cell angles (in these situations, the
Parrinello-Rahman method should be used where available).
The basic idea is to treat the volume V of the cell as a dynamic variable in the system. The Lagrangian of
the system is modified so that it contains a kinetic energy term with a user-defined mass M and a
potential term which is the pV potential derived from an external pressure Pext acting on volume V of the
system.
Parrinello-Rahman method of pressure and stress control
The Parrinello-Rahman method of pressure and stress control can allow simulation of a structure under
externally applied stress. This is useful for studying the stress-strain relationship of materials. Both the
shape and the volume of the cell can change, so that the internal stress of the system can match the
externally applied stress.
The method is discussed in more detail in Parrinello and Rahman, 1981 and is only summarized here.
The Lagrangians of the system are modified such that a term representing the kinetic energy of the cell
depends on a user-defined mass-like parameter W. An elastic energy term pΩ is related to the pressure
and volume or the stress and strain of the system. The equations of motion for the atoms and cell
vectors can be derived from this Lagrangian. The motion of the cell vectors, which determines the cell
shape and size, is driven by the difference between the target and internal stress.
With hydrostatic pressure only:
Eq. CASTEP 37
Where:
h={a•b•c} is the cell vector matrix
G=h'h
r i=hsi
ϕ is the interaction potential
Ω is the volume of the cell
Tr is the trace of a matrix
The dots above some symbols indicate time derivatives and the primes indicate matrix transposition.
With stress, the elastic term pΩ is replaced by:
Eq. CASTEP 38
Where:

S is the applied stress

Ω0 is the initial volume
ε is the strain
ε is also a tensor, defined as:
Note: It is the user-defined variable W, which determines the rate of change of the volume/shape
matrix.
A large W means a heavy, slow cell. In the limiting case, infinite W reverts to constant-volume dynamics.
A small W means fast motion of the cell vectors. Although that may mean that the target stress can be
reached faster, there may not be enough time for equilibration.
NPH ensemble
The constant-pressure, constant-enthalpy ensemble (Andersen, 1980) is the analogue of constant-
volume, constant-energy ensemble, where the size of the unit cell is allowed to vary.
Constraints
CASTEP supports linear constraints defined using the matrix Aij:
Eq. CASTEP 39
The summations are over Ni ions and Nc constraints. Vector Ri is the Cartesian position of the ith atom
and C is a constant. These constraints can be used to, for example:
Fix some of the Cartesian coordinates of the atom
Fix the x-separation between a pair of atoms
Constrain an atom to lie in a plane
Constrain the center of mass to be fixed
Example
The example below (Figure 1) shows the results of an NVE calculation for a nitrogen diatomic molecule
with using a time step of 1 fs. The energy conservation is excellent, the energy drift over 500 steps
(0.5 ps) is less than 0.1 kcal/mole. The power spectrum of the trajectory gives the vibrational frequency
as 2340 cm-1, which is within 1% of the experimental value of 2360 cm-1.

Figure 1. Bond length of the N 2 molecule and power spectrum of the trajectory
Core level spectroscopy

CASTEP can calculate spectroscopic properties of solids that are due to electronic transitions from a core
level of an ion to the conduction band (X-ray absorption) and from the valence band to a core level (X-
ray emission). This can be used to describe a wide variety of experimental results connected to such
processes. Core holes can be created by X-ray or electron incident radiation.
The core level is localized, so core level spectroscopy provides a detailed element-specific picture of the
local electronic structure around a given atomic site. There is no contribution from the other atoms in
the system, so the electronic states for a specific atom can be investigated.
In the case of anisotropic systems, angular-dependent experiments enable the separation of states with
different symmetries for the involved orbitals. An important consequence is that symmetry states,
which result solely from chemical bonding, can be studied.
Emission spectroscopy
X-ray emission spectroscopy (XES) is a classical technique used to study the electronic structure of bulk
samples. It is ideally suited to these systems due to the large information depth (around 0.1 m for soft X-
rays). In XES the core hole created by an X-ray absorption process is filled by the decay of a valence
electron. For this process energy is conserved by the emission of an x-ray photon of matching energy. A
selective, resonant excitation of a core hole state at the atomic center of an adsorbate can be used to
probe surfaces.

Absorption spectroscopy
Electron energy-loss near-edge structure (ELNES or EELS) and x-ray absorption near-edge structure
(XANES) spectroscopies provide information on the unoccupied electronic states by exciting one
electron from a core level into an unoccupied state. Scanning transmission electron microscopes with an
electron energy-loss spectrometer attached have been used extensively in the study of nanoscale
materials, providing information on local composition, structure, and electronic structure. However, the
probing electron or x-ray interacts with a system that has been perturbed by the probe itself. The
system being studied has had an inner-shell electron removed, leaving a core hole.
Core hole effects

The relaxation of a system with a core hole will affect the observed core level excitation spectra so that
interpretation of the experimental spectrum becomes a more challenging task. A satisfactory theory of
optical spectra or core excited spectra should calculate two particle electron-hole interactions in a
reliable and accessible way. In the core level excitation process, the core hole is localized on a single
atomic site. Using an atom with a reduced occupation in the core level in a supercell approximation has
been a good and popular description for the calculation of core level spectroscopy using standard
density functional theory (DFT).
Recent developments in core-level spectroscopy calculations using the Bethe-Salpeter equation or time-
dependent DFT (or a combination of the two) provide more rigorous approaches for a core-level spectra
calculation. In these methods many-body effects, such as the broadening of spectra due to electron-
hole lifetime, can be taken into account in a natural way. While good agreement with experimental
results has been achieved, this necessarily comes with a much greater computational burden in
comparison to standard ground state calculations.
A systematic observation of core hole effects and a quantitative estimation of the core hole strength in
materials can assist in the simulation and interpretation of core level spectra. Applying empirical rules, a
core-level spectrum is not likely to be heavily influenced by core-hole effects, so information on the
ground electronic structure of a material can be inferred directly from the experimental spectrum. In this
case, traditional ground state calculations should predict the main features of experimental results and
allow interpretation of the spectrum. If this is not the case, inclusion of the influence of the core hole is
essential in the theoretical simulation. Analysis of experimental results should take into account that
near-edge fine structure includes influences in the core excitation processes beyond the ground state
electronic structure.
There is an open question regarding the best way of handling the charge of core holes; depending on
the nature of the system it might be appropriate to treat the system either as having lost an electron
and thus having a charge of 1 or as neutral. Materials Studio assumes the former treatment.
Energy broadening
The ELNES calculation can be performed with an energy resolution far better than that used to obtain
experimental results. Therefore, the calculated ELNES must be broadened before comparing it with the
experiment. The broadening observed in the experimental spectra has three origins: the lifetime of the
core hole, the lifetime of the excited state, and instrumental broadening. A good description of this
subject was given by Hebert (2007).
Instrumental broadening is easiest to simulate: it can be modeled by a Gaussian with a FWHM given by
the instrument. For a TEM equipped with a field emission gun, this is usually about 0.6-0.7 eV. Some
instruments are equipped with a monochromator to improve energy resolution to about 0.1 eV. In
nearly all cases the energy distribution can be modeled by a Gaussian curve.

The broadening by the core hole lifetime depends on the atom and the edge. Values for lifetime
broadening are tabulated and can be found in the literature, see Fuggle and Inglesfield (1992).
Broadening due to the lifetime of the core hole is, however, relatively low for edges accessible in EELS
(about 0.2 eV for the Ni or Cu L3 edge). The broadening of core hole lifetimes can be modeled by a
Lorentzian (Fuggle and Inglesfield, 1992).
The broadening by the excited state lifetimes is more complicated. At the edge onset (where the lifetime
of the excited state approaches infinity) the broadening is zero and increases with increasing energy.
Different methods have been employed to obtain the broadening factor, see Hebert (2007) for a
comparative review. An empirical linear function Γ(E) = 0.1 E (where E is the energy above the threshold)
gives good results when compared to the experiment - this is the option employed in CASTEP.
Spin-orbit splitting
Experimental spectra record transitions involving core states that are split as a result of the spin-orbit
interactions; so one should distinguish between states such as p 1/2 and p 3/2 and so on. The CASTEP
implementation lacks spin-orbit terms, so the calculations can only produce "generic" spectra for p, d,
or f states. In spectroscopic terms this means producing (for example) L2,3 spectra rather than just L2.
The simplest, albeit slightly approximate, way to model experimental spectra is to modify the calculated
spectrum as follows:
Find the experimental value of the spin-orbit splitting of the core states.
Generate an approximate L3 spectrum by shifting the L2 spectrum.
Apply intensity scaling based on the occupancy of the respective electronic shell. The intensity ratios
for L spectra are 2:4 and for M spectra 4:6, and so on.
Add the two shifted and scaled spectra together.
For a more general discussion of the core level spectroscopy and details of its implementation see S.-P.
Gao et al. (2008) and references.
Phonon density of states

Phonon density of states (or vibrational density of states) is defined in exactly the same way as the
electronic densities of state, see the DOS equation. The integral over the Brillouin zone goes over all 3N
phonon bands, where N is the number of atoms in the cell. There are two popular conventions
regarding normalization of the phonon DOS. Either it can be normalized to unity or to the total number
of vibrational modes, 3N.
The partial (or projected) phonon density of states is determined as a contribution from the given atom
to the total phonon DOS. This is a useful concept that allows one to understand the nature of various
branches in the phonon spectrum. The contribution to the partial density of states on atom i, from each
phonon band, is evaluated using:
Eq. CASTEP 41
where e j is the eigenvector (normalized to unit length) associated with the mode of energy Ej. The
projected density of states is then obtained by summation of these contributions over all phonon
bands. By construction all the projected phonon DOS sum up to the true phonon DOS.


Formulation of electron localization function
The electron localization function (ELF) was introduced by Becke and Edgecombe as a "simple measure
of electron localization in atomic and molecular systems" (Becke and Edgecombe, 1990). Becke and
Edgecombe associated the localization of an electron with the probability density for finding a second
like-spin electron near the reference point. For small probability densities, D(r) is also small and the
electron is more localized.
Eq. CASTEP 87
The Pauli repulsion between two like-spin electrons, described by the size of D(r), is taken as a measure
of the electron localization. Using the corresponding factor found for a uniform electron gas, Dh(r),
Becke and Edgecombe, defined ELF as:
Eq. CASTEP 88
where
Eq. CASTEP 89
Becke and Edgecombe attributed the ratio χBE(r) to a dimensionless localization index, calibrated with
respect to the uniform electron gas. This reference was chosen arbitrarily, so ELF is only a relative
measure of the electron localization. High ELF values show that at the examined position the electrons
are more localized than in a uniform electron gas of the same density. For example, when η(r) = 1/2 the
effect of the Pauli repulsion is the same as in a uniform electron gas of the same density.
The ELF formulation originates from the Hartree-Fock description of electron gas. A formulation for ELF
in DFT has been developed by Savin et al. (1992). This DFT-ELF approach evaluates the Pauli kinetic
energy density based on the diagonal elements of the one-particle density matrix (the electron density).
The Pauli kinetic energy is the energy due to the redistribution of the electrons in accordance with the
Pauli principle and is the integral of the Pauli kinetic energy density:
Eq. CASTEP 90
The Pauli kinetic energy density itself does not resolve the bonding situation. It is an arbitrary division of
tP(r) by the kinetic energy density of a uniform electron gas of the same electron density, this yields all
the information:

where c F is the Fermi constant:
For a closed shell system the ratio:
is formally identical to the ratio χBE(r) in the HF approximation. The same applies for an open shell
system, where the kinetic energy densities are computed for the corresponding spin part only. So the
ELF formulas based on χBE(r)) and χS(r) are identical. In the interpretation of Savin and coworkers (1992)
ELF is a measure of the influence of Pauli principle as given by the Pauli kinetic energy density, relative to
a uniform electron gas of the same density. Similarly, for the original definition ELF does not mirror tP
(r).
How to interpret ELF

The values of ELF are fairly straightforward to calculate but may not be easy to interpret. The ELF website
(http://www.cpfs.mpg.de/ELF/index.php?content=06interpr.txt) provides a very useful article on
physical meanings of ELF and, in particular, on what ELF is not.
Note: ELF was developed for all electron descriptions. ELF in CASTEP and ONETEP is calculated for
valence electrons only, so it might be less meaningful. In particular, ELF values from CASTEP and
ONETEP do not span the full range from 0 to 1. Extremely localized or delocalized electrons may be
poorly described.
Mulliken population analysis

Mulliken charges and bond populations are calculated according to the formalism described by Segall et
al. (1996a and 1996b).
Introduction
A disadvantage of the use of a plane wave (PW) basis set is that, due to the delocalized nature of the
basis states, it provides no information regarding the localization of the electrons in the system. In
contrast, a Linear Combination of Atomic Orbitals (LCAO) basis set provides a natural way of specifying
quantities such as atomic charge, bond population, charge transfer, and so on.
Population analysis in CASTEP is performed using a projection of the PW states onto a localized basis
using a technique described by Sanchez-Portal et al. (1995). Population analysis of the resulting
projected states is then performed using the Mulliken formalism (Mulliken, 1955). This technique is
widely used in the analysis of electronic structure calculations performed with LCAO basis sets.
Formalism
The eigenstates |ψα(k)>, obtained from the PW calculation when sampling at a given wavevector k, are
projected onto Bloch functions formed from a LCAO basis set |ϕμ(k)>. In general, such a localized basis
set will be neither orthonormal nor complete. Therefore, care must be taken when performing the
projection.
The overlap matrix of the localized basis set, S(k), is defined as:

Eq. CASTEP 63
The quality of the projection may be assessed by calculating a spilling parameter:

Eq. CASTEP 64
Where:
Nα is the number of PW states
wk are the weights associated with the calculated k-points in the Brillouin zone
p(k) is the projection operator of Bloch functions with wavevector k generated by the atomic basis set:
Eq. CASTEP 65
where |ϕμ(k)> are the duals of the LCAO basis, such that:
Eq. CASTEP 66
The spilling parameter varies between one, when the LCAO basis is orthogonal to the PW states, and
zero, when the projected wavefunctions perfectly represent the PW states.
The density operator may be defined:
Eq. CASTEP 67
where nα are the occupancies of the PW states, |χα(k)> are the projected PW states p(k)|ψα(k)> and |χα
(k)> are the duals of these states. From this operator the density matrix for the atomic states may be
calculated as follows:
Eq. CASTEP 68
The density matrix P(k) and the overlap matrix S(k) are sufficient to perform population analysis of the
electronic distribution. In Mulliken analysis (Mulliken, 1955) the charge associated with a given atom, A,
is determined by:
Eq. CASTEP 69
and the overlap population between two atoms, A and B, is:

Eq. CASTEP 70
The weight of a band on a given orbital may be calculated by simply projecting the band onto the
selected orbital. So, the weight of band α on orbital μ is given by:
Eq. CASTEP 71
The contribution of each band α to the density of states is multiplied by the weight Wαμ(k) to get the
projected density of states for orbital μ.
The LCAO Basis Set

In this case, the natural choice of basis set is that of pseudo-atomic orbitals, generated from the
pseudopotentials used in the electronic structure calculation. These are generated automatically when
population analysis is performed. The orbitals are calculated by solving for the lowest energy eigenstates
of the pseudopotential in a sphere, using a spherical Bessel basis set.
By default, the basis set used on an atom of a given species is that of the orbitals in the closed valence
shell of that species. This is usually a sufficiently good basis set for the purposes of population analysis
and partial density of states projection. If the spilling parameter indicates that the basis set does not
represent the PW states with sufficient accuracy, the number of orbitals in the atomic basis set may be
increased. A spilling parameter in the region of a few percent or less is sufficiently good for population
analysis and partial density of states projection. Care should be exercised when increasing the basis set
dramatically, as this can lead to artificial transfers of charge.
Implementation details
The elements of the overlap matrix S(k) are computed in reciprocal space, as the imposition of periodic
boundary conditions implies that the orbitals need only be evaluated on a discrete reciprocal space grid.
The overlaps between orbitals on different atomic sites are calculated on the same grid with the
application of a phase factor. The overlaps between the plane wave states and the basis functions:
Eq. CASTEP 72
are also calculated in reciprocal space as this is the natural representation of the plane wave states.
The duals of the orbitals are constructed as follows:
Eq. CASTEP 73
The duals of the projected wavefunctions are generated in a similar manner:

Eq. CASTEP 74
where R(k) is the overlap matrix between projected states:

Eq. CASTEP 75
Two auxiliary matrices can be defined for efficiency, namely:

Eq. CASTEP 76
and
Eq. CASTEP 77
These matrices are used to calculate the spilling parameter:

Eq. CASTEP 78
Similarly, the density matrix may be straightforwardly calculated as:

Eq. CASTEP 79
In the case of spin dependent systems, the populations of the two spin components are calculated
separately and the sum and difference of the atomic and overlap populations are calculated to find the
net charge and spin, respectively.
Interpreting the results

It is widely accepted that the absolute magnitude of the atomic charges yielded by population analysis
have little physical meaning, since they display a high degree of sensitivity to the atomic basis set with
which they were calculated (Davidson and Chakravorty, 1992). However, consideration of their relative
values can yield useful information (Segall et al., 1996a; Segall et al., 1996b; Winkler et al., 2001),
provided a consistent basis set is used for their calculation.
The spilling parameter should be in the region of a few percent or less in order to ensure that the results
are reliable. If this is not the case, the number of orbitals in the basis set should be increased with care. If
this does not significantly improve the spilling parameter, it may be that atomic orbitals do not provide
a good representation of some of the states in the system.
In addition to providing an objective criterion for bonding between atoms, the overlap population may
be used to assess the covalent or ionic nature of a bond. A high value of the bond population indicates a
covalent bond, while a low value indicates an ionic interaction. A further measure of ionic character may
be obtained from the effective ionic valence, which is defined as the difference between the formal ionic
charge and the Mulliken charge on the anion species. A value of zero indicates a perfectly ionic bond,
while values greater than zero indicate increasing levels of covalency. See Segall et al. (1996b) for more
details.
Care should be taken when interpreting the bond order values for small unit cells. The results will be
incorrect whenever an atom is bonded to a number of periodic images of itself. For example, bond
orders for the primitive cell of silicon are reported as 3.0, while the same calculation for the conventional
cell gives 0.75. The factor of four appears because CASTEP sums up the bond orders for the four bonds

that link the Si atom at the origin with the periodic images of itself, in the primitive cell. A manual
analysis of the multiplicities is required in such cases, specifically: determine the number of bonds to
periodic images of the same atom and divide the bond order by that number.
Note: The physical meaning of Mulliken charges or bond populations for metallic systems is unclear.
This calculation is allowed, but the scientific interpretation of the results will be left to the user.
Hirshfeld charge analysis

Hirshfeld charges (Hirshfeld, 1977) are defined relative to the deformation density, this is the difference
between the molecular and unrelaxed atomic charge densities.
For quantitative descriptions of charge distributions in molecules or solids it is convenient to divide a
system into well-defined atomic fragments. A general and natural choice is to share the charge density at
each point between the atoms, in proportion to their free-atom densities at the corresponding
distances from the nuclei. This prescription yields well-localized bonded-atom distributions each of
which closely resembles the molecular density in its vicinity. Integration of the atomic deformation
densities - bonded minus free atoms - defines the net atomic charges and multipole moments which
concisely summarize the molecular charge reorganization. This permits calculation of the external
electrostatic potential and the interaction energy between molecules or between parts of the same
molecule.
Calculating NMR shielding tensors using pseudopotentials

A uniform external magnetic field, B, applied to a sample induces an electric current. In an insulating
non-magnetic material, only the orbital motion of the electrons contributes to the this current. In
addition, for the field strengths typically used in NMR experiments, the induced electric current is
proportional to the external field, B. This first-order induced current, j(1)(r), produces a non-uniform
magnetic field:
Eq. CASTEP 42
The shielding tensor, σ(r), connects the induced magnetic field to the applied magnetic field:
Eq. CASTEP 43
and the isotropic shielding is given by:

Eq. CASTEP 44
All-electron magnetic response with pseudopotentials

Information about σ(r) at nuclear positions can be obtained from NMR experiments. In CASTEP, the
first-order induced current, j(1)(r), is calculated and then used to evaluate the induced magnetic field, B
(1) through Eq. 42. Calculations are performed with the gauge-including projector augmented-wave
method (GIPAW) developed by Pickard and Mauri (2001). The projector augmented-wave formalism

originally introduced by Blöchl (1994) makes it possible to obtain expectation values of all-electron
operators in terms of pseudo-wavefunctions coming from a pseudopotential calculation and the GIPAW
formalism reconciles the requirement of translational invariance of the crystal in a uniform magnetic
field with the localized nature of Blöchl's projectors. The theory was initially applied with Troullier-
Martins norm-conserving pseudopotentials (Pickard and Mauri, 2001) and has been extended
subsequently to the case of ultrasoft pseudopotentials (Yates, 2007).
The first-order perturbation wavefunction, Ψ(1):
Eq. CASTEP 45
is proportional to the magnetic perturbation, H(1), which, in pseudopotential calculations, contains a

contribution due to the non-locality of the pseudopotential, in addition to the usual term:
Eq. CASTEP 46
Calculation of perturbed wavefunctions

In order to obtain the first-order perturbation wavefunction Ψ(1), the application of the Green function
in Eq. 46 is performed in CASTEP by solving a system of linear equations:
Eq. CASTEP 47
where Q is the projection operator onto the unoccupied Hilbert subspace. The system is solved by a
conjugate gradient minimization scheme, whereby the tedious summation over unoccupied states is
avoided. The method is, thus, comparable in computational cost to the calculation of the ground-state
electronic structure.
NMR properties of molecules and crystals

The calculation of the induced current involves evaluation of expectation values of the position
operator, whose definition for extended systems is not straightforward. Two approaches have been
developed (Pickard and Mauri, 2001) and implemented in CASTEP. For translationally invariant systems
with well-defined Blöch vectors, k, the application of the position operator can be reduced to calculating
the gradient in k-space. Alternatively, for finite systems, which are represented by supercell structures (a
molecule in a box) in CASTEP, one can apply a real-space representation of the position operator. The
artificial periodicity imposed on the system causes the position operator to acquire a sawtooth shape.
Thus, in the vicinity of the box boundaries, the position operator is distorted. Because of this, a
sufficiently large supercell must be constructed so that the electronic density does not reach the regions
where the position operator behaves unphysically. This condition is easily satisfied by the usual physical
requirement that the molecules in neighboring boxes do not interact.
NMR shielding tensor

Finally, the induced magnetic field, B(1), is calculated from the induced current and its value at the
nuclear position determines the NMR shielding tensor. The calculated tensor is rather sensitive to
numerical errors in both the unperturbed wavefunction, Ψ(0), and its first-order perturbation,Ψ(1), so
the convergence requirements for NMR calculations are more stringent than, for example, routine band
structure calculations. To obtain reliable results, the convergence of the wavefunction with respect to

the number of basis functions (plane waves) must be ensured and a well-converged conjugate gradient
procedure put in place to determine the coefficients of the plane waves. Apart from that, in calculating
solid-state NMR properties (a small unit cell as opposed to a molecule in a box) the convergence of the k-
space sum over the Brillouin zone must be achieved. The NMR observables are not particularly sensitive
to uncertainties in the ground-state density distribution in the system, which determines the
unperturbed Hamiltonian. Here, the usual convergence criteria for self-consistent DFT calculations are
sufficient.
Chemical shift (or shielding) can be calculated for paramagnetic materials where the total spin is zero,
even if a spin-polarized treatment is applied. This opens the possibility of using the DFT+U method as
implemented by Shih and Yates (2017). The nonlocal Hubbard correction potential has been reexamined
in order to comply with the gauge-including projector augmented-wave transformation under an
external uniform magnetic field. The resulting expression is suitable for chemical shift calculations using
both norm-conserving and ultrasoft pseudopotentials in the projector augmented-wave scheme. As a
result more accurate results can be obtained for transition metal and rare earth oxides.
Note: It is important to examine the results and establish that the solution is indeed paramagnetic. If
the total spin of the final state is non-zero, or the spin arrangement is antiferromagnetic, the results
are likely to be meaningless.
Sensitivity of NMR to calculation parameters

NMR properties calculations are very sensitive to the number of k-points in the Brillouin zone. It is hard
to construct a general rule for the number of k-points required, so it is recommended that you carry out
convergence tests. An example convergence test for gallium phosphide is given below (these results are
obtained for the experimentally observed structure of cubic GaP, ultra-fine settings, on the fly generated
ultrasoft pseudopotentials, PBE functional).
Table 1. Convergence test for GaP
k-point mesh chemical shift (ppm)

P 2×2×2 -578.60
4×4×4 302.72
8×8×8 376.18
12 × 12 × 12 375.45
16 × 16 × 16 375.34
Ga 2×2×2 920.61
4×4×4 1335.72
8×8×8 1352.50
12 × 12 × 12 1352.21
16 × 16 × 16 1352.20
It follows from Table 1 that a grid of at least 12 × 12 × 12 is required to achieve convergence of the
chemical shift to within 1-2 ppm, and finer grids might be needed to achieve higher accuracy.
NMR properties are very sensitive to atomic positions, which makes NMR such a useful experimental
tool for structure analysis. This implies that it is highly recommended to perform a geometry

optimization run prior to the NMR calculation. If the structure of a crystal or molecule under
investigation is obtained from an experimental study, it is advisable to optimize positions of hydrogen
atoms first of all. If the forces on heavy atoms as reported by CASTEP are high (in excess of 1 eV/Å) then
complete structure optimization is recommended.
NMR J-couplings
NMR J-coupling or nuclear spin-spin coupling is an indirect interaction of the nuclear magnetic moments
mediated by the bonding electrons. It is manifested as the fine structure in NMR spectra, providing a
direct measure of bond strength and a map of the connectivities of the system.
The J-coupling mechanism is an essential component of many NMR experiments. Joyce et al. (2007)
developed a method to calculate J-coupling constants from first-principles in extended systems in a
planewave-pseudopotential density functional theory framework, using the projected augmented wave
method (PAW) to reconstruct the all-electron properties of the system. This method has been validated
for a small number of systems containing light atoms against quantum chemical calculations and against
experimental data (see for example, Joyce et al., 2008). This technique has been further developed by
Green and Yates (2014) to incorporate scalar relativistic effects in the ZORA (zeroth-order regular
approximation) approach and hence to provide a highly efficient method for predicting J-coupling in
extended systems containing heavy ions at negligible extra computational cost compared to the non-
relativistic method.
A general review of the formalism is given by Yates (2010), this discusses various aspects of the
calculations which should be taken into account when comparing results with solid-state NMR
experiments including anisotropy and orientation of the J tensors, the reduced coupling constant, and
the relationship between the J-coupling and crystal structure.
J-coupling interactions can be decomposed into four mechanisms:
two due to interactions of the electron spins with the nuclear moments
two due to electron currents induced by the nuclear moments
When spin-orbit coupling is neglected these can be treated separately.
The spin term can be decomposed into an analog of a spin-dipole interaction plus a Fermi-contact term,
which is due to the finite probability of the presence of an electron at the nucleus.
Induced current operators can be decomposed into diamagnetic and paramagnetic current operators.
Joyce et al. (2007) found that the Fermi-contact contribution to be consistently the largest component,
while the diamagnetic and spin-dipolar contributions were very small for all the cases studied.
Experimental interest is focused primarily on the isotropic coupling constant which is obtained from the
trace of the J-coupling tensor and is measured in Hertz. Recent extensive validation studies (for example,
by Green and Yates 2014) demonstrate that the pseudopotential PAW approach for J-coupling
calculations gives results in good qualitative and quantitative agreement with experiment both for light
and heavy elements.
It is important to note that solid state calculations of J-couplings using CASTEP correctly account for
long-range effects in the periodic systems and reproduce the differences between solution and solid-
state values (Joyce et al., 2008).

Note: Induced magnetization density and current density are expected to be short-ranged. This
forms the basis of using J-coupling as a tool for probing the strength of interatomic bonds. However,
in a periodic calculation the perturbing nucleus can be viewed as similar to a defect in a defect
calculation. Hence, sometimes it might be necessary to construct a supercell which is large enough to
inhibit the interaction between the periodic defects or perturbations. Convergence with respect to
the cell size should represent an important test in establishing accuracy of J-coupling calculations in
either periodic systems or in molecule in a box calculations.
EPR G-tensor
Electron Spin Resonance (EPR - also known as Electron Paramagnetic Resonance) is a powerful
experimental probe of the structure of defects in solids. EPR spectra of spin ½ centers are made up of
two contributions:
the hyperfine parameters
the g-tensor
The g-tensor arises from the interaction of the electronic spin with external magnetic field. This term
plays a somewhat similar role to the shielding in NMR; induced electronic currents in the sample modify
the g tensor from its vacuum value.
EPR spectrum can be modeled using the following effective Hamiltonian, bilinear in the total electron
spin S, and the applied uniform magnetic field or nuclear spins, B and II, respectively:
where:
atomic units are used
α is the fine structure constant
the summation I runs over the nuclei
The tensors AI are the hyperfine parameters, and the tensor g is the EPR g-tensor.
The Gauge Including Projector Augmented Waves (GIPAW) approach has been used to compute g
tensors in several crystalline materials including defects in α-quartz and zirconia.
The hyperfine tensor can be obtained from the ground state charge density. In CASTEP it is computed
using the PAW approach of Van de Walle and Blöchl (1993). The calculation of the g-tensor is more
involved, requiring the linear response currents. These are computed using the GIPAW approach of
Pickard and Mauri (2001). The total g-tensor is obtained as:
Where the contributions to the total change in the g-tensor are the electron Zeeman kinetic energy,
spin-orbit, and the spin-other-orbit correction. The calculation of these terms follows the approach of
Pickard and Mauri (2002) extended for the use of ultrasoft potentials by Yates et al. (2007). The GIPAW
approach has been used to compute g-tensors in several crystalline materials including defects in quartz
and zirconia by Pietrucci et al. (2006).
Optical properties
Definition of optical constants
CASTEP can calculate the optical properties of solids that are due to electronic transitions.

In general, the difference in the propagation of an electromagnetic wave through vacuum and some
other material can be described by a complex refractive index, N:
Eq. CASTEP 48
In vacuum N is real, and equal to unity. For transparent materials it is purely real, the imaginary part
being related to the absorption coefficient by:
Eq. CASTEP 49
The absorption coefficient indicates the fraction of energy lost by the wave when it passes through the
material, so that the intensity at the distance x from the surface is:
where I(0) is the intensity of the incident light.

The reflection coefficient can be obtained for the simple case of normal incidence onto a plane surface by
matching both the electric and magnetic fields at the surface:
Eq. CASTEP 50
However, when performing calculations of optical properties it is common to evaluate the complex
dielectric constant and then express other properties in terms of it. The complex dielectric constant, ε
(ω), is given by:
Eq. CASTEP 51
and hence the relation between the real and imaginary parts of the refractive index and dielectric
constant is:
Eq. CASTEP 52
Another frequently used quantity for expressing optical properties is the optical conductivity, σ(ω):
Eq. CASTEP 53
Optical conductivity is usually used to characterize metals, however CASTEP is aimed more toward the
optical properties of insulators and semiconductors. The main difference between the two is that
intraband transitions play important role in the IR part of the optical spectra of metals and these
transitions are not considered at all in CASTEP.
A further property that can be calculated from the complex dielectric constant is the energy loss
function. It describes the energy lost by an electron passing through a homogeneous dielectric material
and is given by:

Eq. CASTEP 54
Connection to experimental observables

Experimentally, the most accessible optical parameters are the absorption, η(ω), and the reflection, R
(ω), coefficients. In principle, given the knowledge of both of these, the real and imaginary parts of N can
be determined, through Eq. CASTEP 49 and Eq. CASTEP 50. Eq. CASTEP 51 allows expression in terms of
the complex dielectric constant. However, in practice, the experiments are more complicated than the
case of normal incidence considered above. Polarization effects must be accounted for and the
geometry can become quite complex (for example, transmission through multilayered films or incidence
at a general angle).
CASTEP supports spin-polarized calculations of optical properties for magnetic systems. Only transitions
between the states with the same spin are allowed. For a more general discussion of the analysis of
optical data see Palik (1985).
Connection to electronic structure
The interaction of a photon with the electrons in the system is described in terms of time dependent
perturbations of the ground state electronic states. Currently CASTEP provides two approaches to
optical properties calculations; one is based on standard DFT Kohn-Sham orbitals and the other uses
more accurate but much more time-consuming time-dependent DFT (TD-DFT) theory.
DFT optics
In this approach excited states are represented as unoccupied Kohn-Sham states. Transitions between
occupied and unoccupied states are caused by the electric field of the photon (the magnetic field effect is
weaker by a factor of v/c). When these excitations are collective they are known as plasmons (which are
most easily observed by the passing of a fast electron through the system rather than a photon, in a
technique known as Electron Energy Loss Spectroscopy, described by Eq. CASTEP 54 , since transverse
photons do not excite longitudinal plasmons). When the transitions are independent they are known as
single particle excitations. The spectra resulting from these excitations can be thought of as a joint
density of states between the valence and conduction bands, weighted by appropriate matrix elements
(introducing selection rules).
Evaluation of the dielectric constant

CASTEP calculates the imaginary part of the dielectric constant, which is given by:
Eq. CASTEP 55
where u is the vector defining the polarization of the incident electric field.
This expression is similar to Fermi's Golden rule for time dependent perturbations, and ε2(ω) can be
thought of as detailing the real transitions between occupied and unoccupied electronic states. Since
the dielectric constant describes a causal response, the real and imaginary parts are linked by a Kramers-
Kronig transform. This transform is used to obtain the real part of the dielectric function, ε1(ω).

Details of the calculation

Evaluation of matrix elements
The matrix elements of the position operator that are required to describe the electronic transitions in
Eq. CASTEP 55 may normally be written as matrix elements of the momentum operator allowing
straightforward calculation in reciprocal space. However, this depends on the use of local potentials
(Read and Needs, 1991), while in CASTEP nonlocal potentials are more often used. The corrected form of
the matrix elements is:
Eq. CASTEP 56
Ultrasoft pseudopotentials produce an additional contribution to optical matrix elements that is also
included in CASTEP results.
Drude correction
The intraband contribution to the optical properties affects mainly the low energy infrared part of the
spectra. It can be described sufficiently accurately using a semiempirical Drude term in the optical
conductivity:
Eq. CASTEP 57
in terms of the plasma frequency ωP and damping parameter γD which depends on many details of the
material and is usually obtained from experiment. The Drude damping parameter describes the
broadening of the spectra due to effects not included in the calculation. Examples of processes that
contribute to this broadening are electron-electron scattering (including Auger processes), electron-
phonon scattering, and electron-defect scattering. This last contribution is usually the most important.
As a result an a priori determination of the broadening would require knowledge as to the
concentrations and kinds of defects present in the sample under study.
Polarization
For materials that do not display full cubic symmetry, the optical properties will display some
anisotropy. This can be included in the calculations by taking the polarization of the electromagnetic
field into account. As mentioned above, the unit vector u defines the polarization direction of the
electric field. When evaluating the dielectric constant there are three options:
polarized: requires a vector to define the direction of the electric field vector for the light at normal
incidence to the crystal.
unpolarized: requires a vector to define the direction of propagation of incident light at normal
incidence to the crystal. The electric field vector is taken as an average over the plane perpendicular
to this direction.
polycrystal: no direction need be specified, the electric field vectors are taken as a fully isotropic
average.
Scissors operator
As discussed below, the relative position of the conduction to valence bands is erroneous when the
Kohn-Sham eigenvalues are used. In an attempt to fix this problem, inherent in DFT, a rigid shift of the

conduction band with respect to the valence band is allowed. This procedure of artificially increasing the
band gap is know as a scissor operator.
Limitations of the method

Local field effects
The level of approximation used here does not take any local field effects into account. These arise from
the fact that the electric field experienced at a particular site in the system is screened by the
polarizability of the system itself. So, the local field is different from the applied external field (that is, the
photon electric field). This can have a significant effect on the spectra calculated (see the example of bulk
silicon calculation below) but it is prohibitively expensive to calculate for general systems at present.
Quasiparticles and the DFT bandgap
In order to calculate any spectral properties it is necessary to identify the Kohn-Sham eigenvalues with
quasiparticle energies. Although there is no formal connection between the two, the similarities
between the Schrödinger-like equation for the quasiparticles and the Kohn-Sham equations allow the
two to be identified. For semiconductors, it has been shown computationally (by comparing GW and
DFT band structures) that most of the difference between Kohn-Sham eigenvalues and the true
excitation energies can be accounted for by a rigid shift of the conduction band upward with respect to
the valence band (Godby et al., 1992). This is attributed to a discontinuity in the exchange-correlation
potential as the system goes from (N)-electrons to (N+1)-electrons during the excitation process. There
can, in some systems, be considerable dispersion of this shift across the Brillouin zone, and the scissor
operator used here will be insufficient.
Excitonic effects
In connection with the absence of local field effects, excitonic effects are not treated in the present
formalism. This will be of particular importance for ionic crystals (for example NaCl) where such effects
are well known.
Other limitations
The nonlocal nature of the GGA exchange-correlation functionals is not taken into account when
evaluating the matrix elements but it is expected that this will have a small effect on the calculated
spectra.
Phonons and their optical effects have been neglected.
Finally, there is an intrinsic error in the matrix elements for optical transition due to the fact that
pseudowavefunctions have been used (that is they deviate from the true wavefunctions in the core
region). However, the selection rules will not be changed when going from pseudo- to all-electron
wavefunctions.
Sensitivity of optical properties to calculation parameters

Number of conduction bands
This parameter defines the energy range covered in the calculation, and it also determines the accuracy
of the Kramers-Kronig transform. It is clear from Figure 1 that ε2(ω) converges rapidly with the number
of conduction bands included.

Figure 1. Convergence of the dielectric function with the number of conduction bands
Energy cutoff
The value of the energy cutoff that was used in the original SCF calculation of the ground state electron
density is an important factor that determines the accuracy of the calculated optical properties. A bigger
basis set provides more accurate self-consistent charge density and more variational freedom when
searching for wavefunctions of unoccupied states. Figure 2 shows that while it is important to converge
the calculation with respect to the planewave cutoff to obtain the correct energies for the spectral
features, the shape of those features is reached rapidly.

Figure 2. Convergence of the dielectric function with the cutoff energy
Number of k-points in the SCF calculation

The accuracy of the ground state electron density depends on the number of k-points used in the SCF
run as well as on the basis set quality. Figure 3 reveals that the optical properties converge rapidly with
the number of k-points used in the SCF run, which implies low sensitivity to the details of the charge
density.

Figure 3. Convergence of the dielectric function with the number of k-points in the SCF calculation
Number of k-points for Brillouin zone integration

It is important to use a sufficient number of k-points in the Brillouin zone when running optical matrix
element calculations. The matrix element changes more rapidly within the Brillouin zone than electronic
energies themselves. Therefore, one requires more k-points to integrate this property accurately than
are needed for an ordinary SCF calculation. Figure 4 clearly demonstrates the importance of converging
the Brillouin zone integration for the optical properties with respect to the k-point density. Both
energies and spectral features are strongly affected by the accuracy of this integration.

Figure 4. Convergence of the dielectric function with the number of k-points in the optical matrix elements
calculation
TD-DFT optics
TD-DFT is a formally exact treatment of electronic excited states. The implementation in CASTEP follows
the work of Hutter (2003), which takes a linear response approach to computing excitation energies
directly. A benefit of this method is that the response wavefunctions for excited states are calculated
and can then be used to derive further properties such as optical matrix elements and atomic forces. In
the case of atomic forces, a geometry optimization or molecular dynamics run can be performed for a
chosen excitation.
Hutter reformulated the equations of time-dependent Hartree-Fock in the Tamm-Dancoff
approximation applied to TD-DFT (Hirata and Head-Gordon, 1999) so that they could be efficiently
implemented in a plane-wave basis set. This self-consistent eigenvalue problem is solved in CASTEP by
the user’s choice of conjugate gradient or block-Davidson minimizers. The result is a set of electronic
excitation energies and linear response wavefunctions.
A technical report on the implementation details of the TD-DFT minimizers can be found at
http://www.hector.ac.uk/cse/distributedcse/reports/castep02/.
A second report on the implementation of excited state forces can be found at
http://www.hector.ac.uk/cse/distributedcse/reports/castep03/.
Phonons
The basic theory of phonons, or lattice vibrations, in crystals is well understood and has been described
in detail in text books such as those by Born and Huang (1954) and Ashcroft and Mermin (1976). The
importance of the phonon interpretation of lattice dynamics is illustrated by the large number of

physical properties that can be understood in terms of phonons: infrared, Raman, and neutron
scattering spectra; specific heat, thermal expansion, and heat conduction; electron-phonon interactions
and, thus, resistivity and superconductivity, and so on.
A number of approximations are made in order to arrive at the phonon description of lattice vibrations.
First of all, it is assumed that the mean equilibrium position of each ion, i, is a Bravais lattice site, Ri.
Secondly, it is assumed that the amplitude of atomic displacements is small compared to interatomic
distances. This leads to a harmonic approximation which is sufficiently accurate to describe most of the
lattice dynamical effect of interest. However, further refinement, in the form of anharmonic theory, is
required to explain physical properties at elevated temperatures when the harmonic approximation
breaks down.
The N-ion harmonic crystal can be considered as 3N independent harmonic oscillators, whose
frequencies are those of 3N classical normal modes. Thus, at each wave vector, q, in the Brillouin zone
there are 3N vibrational modes. There are two equivalent descriptions of this system, either in terms of
normal modes or phonons. Phonons are the quanta of the ionic displacement field that describe
classical sound; they are similar to photons, the quanta of the radiation field that describe classical light.
The properties of phonons can be described using a harmonic approximation based on the knowledge
of just one fundamental quantity, the force constants matrix:
Eq. CASTEP 58
Here u refers to the displacement of a given atom and E is the total energy in the harmonic
approximation. This force constants matrix (or Hessian matrix) can also be represented in reciprocal
space and the result is commonly referred to as the dynamical matrix:
Eq. CASTEP 59
Classical equations of motion can be written in the language of dynamical matrices, as an eigenvalue
problem. Each atomic displacement is described in the form of plane waves:
Eq. CASTEP 60
where the polarization vector of each mode, ε, is an eigenvector with the dimension of 3N of the
eigenvalue problem:
Eq. CASTEP 61
The dependence of the frequency, ω, on the wave vector is known as the phonon dispersion.
Each lattice always has three acoustic modes. Their dispersion relation at small values (near the Γ point)
is linear, which is characteristic of sound waves. The rest of the vibrational modes, 3N - 3, in a Bravais
lattice with basis are known as optical modes because the long wavelength optical modes in ionic
crystals can interact with electromagnetic radiation and are therefore responsible for much of the
characteristic optical behavior of such crystals. The frequencies of optical modes are finite at q = 0. A
simplistic characterization of acoustic and optical branches (Ashcroft and Mermin, 1976) would be: All
ions in a primitive cell move essentially in phase in an acoustic mode and the dynamics is determined by
the interaction between cells; an optical mode is one in which the ions within each cell exhibit a

molecular vibration mode which is broadened into a band of frequencies due to intercellular
interactions.
A popular way of classifying lattice vibrations is based on the relationship between the orientation of the
polarization vector, ε, and the propagation direction, q. In an isotropic medium for the case of a
monatomic primitive cell it is always possible to choose three solutions for a given q so that one branch
(longitudinal) is polarized along the propagation direction and the other two branches (transverse) are
polarized perpendicular to this direction. This simple relationship does not hold for an arbitrary q-vector
in an anisotropic crystal, nor for a Bravais lattice with basis. It is still common to classify vibrational
modes along high symmetry directions in simple lattices based on the transverse and longitudinal
description.
Long wavelength vibrations in polar materials deserve a special mention. The long range character of the
Coulomb forces gives rise to macroscopic electric fields for longitudinal optic (LO) phonons at the Γ-point
in polar semiconductors and insulators. The coupling between longitudinal phonons and the
nonperiodic electric field gives rise to LO-TO splitting at the Γ-point. The value of the splitting is
determined by the static dielectric constant of the crystal and by the Born effective charge of the ions.
The Born effective charge tensor of the sth ion is the partial derivative of the macroscopic polarization
with respect to a periodic displacement of all the periodic images of that ion at zero macroscopic electric
field. A good review of the practical methods of dealing with this effect is given by Baroni et al., (2001).
Thermodynamic properties of crystals can be evaluated in a fairly straightforward way based on a
knowledge of the phonon frequencies across the Brillouin zone (see Ashcroft and Mermin, 1976; Baroni
et al., 2001). These quasiharmonic results are quite accurate at moderate temperatures and only small
corrections to calculated phase transition properties can be found at temperatures as high as 1000-
2000 K (Kern et al., 1999).
Practical schemes for phonon calculations

A good review of the existing schemes can be found in Baroni et al., (2001). The theoretical study of
phonon properties has to rely on one of the three available methods for determining the force
constants matrix: analytical calculations, supercell calculations, or linear response calculations. The
analytical approach is only viable when the energy model is sufficiently simple to allow a direct
evaluation of the second derivatives of the energy with respect to atomic displacements (for example,
empirical pair potential models). Therefore, it is unsuitable for first principles calculations. Further
alternatives such as extracting vibrational properties from molecular dynamics runs (Arias et al., 1992)
are less transparent and noticeably more computationally expensive.
The supercell method involves perturbing the positions of the atoms slightly and calculating the reaction
forces (Ackland et al., 1997). It is necessary to use supercells of the original cell when interatomic
interaction in the system is long ranged. The main advantage of this method (and of the closely related
frozen phonon technique) is that there is no need for a new formalism; any total energy scheme like
CASTEP can be used to evaluate the forces at a number of carefully selected distorted configurations.
The original frozen phonon scheme requires a displacement with the given wave vector and has been
successfully used since the early 1980s (Yin and Cohen, 1982; Ho et al., 1984). The force constants matrix
evaluation in this formalism has been used to calculate interplanar force constants (Wei and Chou, 1994)
and, thus, phonon dispersion along high symmetry directions. More recent applications are based on
the full reconstruction of the force constants matrix (Ackland et al., 1997; Parlinski et al., 1997; and
references in Baroni et al., 2001).
Linear response calculations seek to evaluate the dynamical matrix directly for a set of q-vectors. The
starting point of the linear response approach is evaluation of the second-order change in the total
energy induced by atomic displacements. The main advantage of the scheme is that there is no need to
artificially increase the cell size in order to accommodate small values of the q-vectors, as in the frozen

phonon method, or to overcome the long range interaction problem (force constants matrix from
supercell calculations). A more detailed description of the linear response method can be found in
Baroni et al., (2001). The CASTEP implementation is described in the Linear response topic.
Interpolation schemes
The force constant matrix (Eq. CASTEP 58) for non-polar insulators and most metals decays
proportionally to r-5 or even faster. This fact allows the introduction of an effective interpolation scheme
to accelerate phonon calculations within both the finite displacement and linear response formalisms
through the introduction of a cutoff radius, Rc, beyond which all the elements of the force constant
matrix can be treated as zero. If an approximation for the force constant is available, the dynamical
matrix for any given reciprocal vector can be calculated using Eq. CASTEP 59.
Finite displacement: supercell method
In the supercell method, finite displacement calculations are carried out in the supercell, circumventing
the sphere described by the cutoff radius, which directly give all the non-zero elements of the force
constant matrix.
Linear response: Fourier interpolation
In the Fourier interpolation method, calculations are performed on the regular reciprocal mesh (with a
spacing corresponding to the real space cutoff radius). The set of dynamical matrices obtained in these
calculations can be used to construct the force constant matrix using Fourier transformation.
Symmetry analysis of vibrations

Symmetry considerations in vibrational analysis are useful for various reasons. For example, the use of
symmetry in the CASTEP implementation reduces computational time and the automatic assignment of
spectroscopic labels allows you to interpret experimentally measured modes at Γ-points with greater
confidence. Symmetry analysis and the subsequent enforcing of symmetry is carried out along the lines
suggested by Warren and Worlton (1974). The nomenclature suggested by these authors for labeling
symmetry elements is adopted in the CASTEP output. The notation for irreducible representation labels
that are common in spectroscopic analysis is specified by IUPAC recommendations (1997).
Infrared spectra
In the infrared energy range (typically below 1 eV), vibrations are an important component of optical
spectra. In the case of metals, this process is screened considerably by the plasmon (intraband)
electronic contribution, while for semiconductors and insulators, it is vibrations that are mainly
responsible for absorbing light energy.
Theoretically, infrared absorption intensities are described in terms of a dynamical matrix (also known as
a Hessian) and Born effective charges (also known as atomic polarizability tensors, ATP). The Born
effective charge tensor of an ion is the partial derivative of the macroscopic polarization with respect to a
periodic displacement of all the periodic images of that ion at zero macroscopic electric field. A good
review of the practical methods of dealing with this effect is given by Baroni et al. (2001). The Born
effective charge tensor is calculated within the linear response formalism by applying a Gonze
approximation. Once these data are known, it is straightforward to calculate IR intensities (see
Calculating vibrational frequencies). IR absorption intensities are printed in the CASTEP output file for
any run where phonons at the Γ-point and LO-TO splitting are calculated.
The concept of IR absorption intensities is mostly used in the analysis of molecules. CASTEP can be used
to model isolated molecules if the molecule in question is assumed to be contained within a box (see
Setting up a calculation on an isolated molecule. This approach allows accurate prediction of IR

absorption intensities. Figure 1 compares the results of such calculations obtained using DMol3 and
CASTEP for a variety of molecules.
Figure 1. Comparison of IR spectra calculated using DMol3 and CASTEP for a range of molecules
Linear response
Linear response, or density functional perturbation theory (DFPT), is one of the most popular methods
of ab initio calculation of lattice dynamics (Baroni et al. 2001). However, the applicability of the method
extends beyond the study of vibrational properties. Linear response provides an analytical way of
computing the second derivative of the total energy with respect to a given perturbation. Depending on
the nature of this perturbation, a number of properties can be calculated. A perturbation in ionic
positions gives the dynamical matrix and phonons; in magnetic field - NMR response; in unit cell vectors
- elastic constants; in an electric field - dielectric response, and so on.
The force constants matrix can be obtained by differentiating the Hellmann-Feynman forces on atoms,
with respect to ionic coordinates. This procedure reveals that the force constants matrix depends on the
ground state electron charge density and on its linear response to a distortion of atomic positions. Due

to the variational principle of the density functional formalism, the second order change in energy
depends on the first order change in the electron density.
The DFPT formalism is, in many ways, very similar to the density functional theory (DFT) itself. DFT states
that the total energy is the functional of the electron density; thus one can solve the DFT equations by
minimizing the total energy. Similarly, the DFPT problem can be solved by minimizing the second order
perturbation in the total energy, which gives the first order changes in density, wavefunctions and
potential (Gonze et al. 1994, Gonze 1997).
This variational technique for solving DFPT problems is a more robust and accurate method than the
original Green's function, iterative scheme suggested by Baroni et al. 1987. Both methods should
converge to the same solution but the Green's function method does not rely on the variational
principle and its convergence properties are thus inferior. Moreover, once the first order change in
wavefunctions, ψ(1), is evaluated, then the Green's function scheme evaluates the second order energy,
which is not stationary with respect to first-order errors in ψ(1). Thus, the variational scheme of Gonze
1997 is expected to be more accurate.
The electronic second order energy, which is minimized in this approach, as implemented in CASTEP, is:
Eq. CASTEP 62
where the superscripts refer to the ground state (0) and first (1) and second (2) order changes,
respectively. Similar terms have to be evaluated for the ionic terms in the total energy. The
preconditioned conjugate gradients minimization scheme can be used to find the minimum of this
functional with respect to the first order wavefunctions. The dynamical matrix for a given q is then
evaluated from the converged first order wavefunctions and densities (Gonze 1997).
Raman spectra
Raman spectroscopy is used to study the vibrational, rotational, and other low-frequency modes in a
system. It is based on the Raman effect of inelastic scattering of monochromatic light. This interaction
with vibrations results in the energy of incident photons being shifted up or down. The energy shift is
defined by the vibrational frequency and the proportion of the inelastically scattered light is defined by
the spatial derivatives of the macroscopic polarization, technical details are described by Porezag and
Pederson (1996).
Spatial derivatives of the macroscopic polarization are calculated numerically along eigenvectors of each
Raman active phonon mode by calculating the polarization for each displacement using a linear
response formalism. Once these derivatives are known, it is straightforward to calculate the Raman
cross-section through appropriate space averaging.
Raman activities defined by Porezag and Pederson (1996) characterize phonon mode contributions to
the intensity of peaks in Raman spectra. These intensities depend on some other factors such as the
temperature and incident light wavelength. It is important to specify these parameters in order to
simulate a realistic Raman spectrum that can be compared to experimental results.
The Raman susceptibility tensor from which the Raman intensity can be calculated is defined as:

where:
χ(1) is the first order dielectric susceptibility
ν is a phonon eigenvector (the direction in which atoms, I, at equilibrium positions R, move under
excitation of a phonon mode, m in a unit cell with volume V)
Greek subscripts denote Cartesian directions
The derivative of χ(1) inside the sum can be calculated in CASTEP using a finite difference approach,
making small atomic displacements corresponding to the eigenvectors of each Raman active mode.
However, the derivative can be written in full as:
where:
ϵ is the electric field of a photon in a Raman experiment exciting the phonon
E is the total energy of the system.
We can use the (2n+1) theorem in quantum mechanics to evaluate this in a more direct manner, see
Miwa (2011). This theorem states that, under a perturbation, if the perturbed wavefunctions are known
to order n then we can evaluate the perturbed energy up to order 2n+1. In particular, in a CASTEP
phonon calculation, we need to evaluate the perturbed wavefunctions up to first order and therefore
we should have access to the 3rd order energy perturbation, E(3), from which we can compute the
susceptibility derivatives.
For Raman intensities, the full expression for this third derivative is given by equations (28)-(31) of Miwa
(2011). These expressions are implemented in CASTEP for norm-conserving pseudopotentials.
The finite difference method and the "2n+1" linear response method lead to the same Raman
susceptibility tensor, however the mathematical, and hence computational, routes are rather different.
In the finite difference method, the phonon eigenvectors are calculated during a phonon task, and are
then used to calculate the third order derivative for each mode one at a time. This means that there is a
separate Raman intensity calculation for each Raman active mode to obtain its intensity.
Computationally, this is usually the most time consuming part of a Raman intensity calculation.
Alternatively, in the linear response method, we first precompute the 9 second order derivatives with
respect to electric field: equation 19 of Miwa (2011) and then construct the full set of Raman tensors
during the phonon perturbations: equation (28) of Miwa (2011). Computationally, this means that in the
linear response Raman intensity method there is an initialization stage and each phonon perturbation
calculation has slightly more work to do than in the finite difference method. However, the
computational work is then complete, unlike in the finite difference method where additional electric
field perturbations are required for every Raman intensity.
For small cells the linear response method will be slower as the initialization stage and the extra cost of
each phonon perturbation does not outweigh the effort of calculating the finite difference Raman
tensor. For example, a linear response calculation for the primitive cell of boron nitride in the diamond
structure takes about twice as long as the finite displacement calculation. However, the linear response
method quickly becomes significantly more efficient as the number of degrees of freedom increases.
Calculations for molecular crystals containing 50-100 atoms per unit cell can be an order of magnitude
faster using the linear response method compared to the finite difference method.
Note: It is important to remember that Raman intensities are effectively third order derivatives, so to
obtain reasonable results very accurate calculations are required. Both the energy cutoff and k-point
sampling can contribute significantly to a convergence error, so a careful convergence test is
necessary to obtain reliable Raman intensities.

Thermodynamic calculations
The results of a calculation of phonon spectra can be used to compute energy (E), entropy (S), free
energy (F), and lattice heat capacity (Cv) as functions of temperature. The CASTEP total energy yields the
total electronic energy at 0 K. The vibrational contributions to the thermodynamic properties are
evaluated to compute E, S, F, and Cv at finite temperatures as discussed below.
Note: Thermodynamic calculations can be performed only if the system is in the ground state, that is,
geometry optimization is fully converged. This means that all the phonon eigenfrequencies must be
real and non-negative.
When you perform a vibrational analysis with CASTEP the results of the thermodynamic calculations can
be visualized using the thermodynamic analysis tools.
The formulas below are based on work by Baroni et al. (2001).
The temperature dependence of the energy is given by:
Eq. CASTEP 80
where Ezp if the zero point vibrational energy, k is the Boltzmann constant, ħ is the Planck constant and
F(ω) is the phonon density of states. Ezp can be evaluated as:
Eq. CASTEP 81
The vibrational contribution to the free energy, F, is given by:

Eq. CASTEP 82
The vibrational contribution to the entropy, S, can be obtained using:

Eq. CASTEP 83
The lattice contribution to the heat capacity, Cv, is:

Eq. CASTEP 84
A popular representation of the experimental data on heat capacity is based on the comparison of the
actual heat capacity to that predicted by the Debye model. This leads to the concept of the temperature

dependent Debye temperature, ΘD(T). Heat capacity in Debye model is given by (Ashcroft and Mermin,
1976):
Eq. CASTEP 85
where N is the number of atoms per cell. Thus, the value of the Debye temperature, ΘD, at a given
temperature, T, is obtained by calculating the actual heat capacity, Eq. CASTEP 84, then inverting Eq.
CASTEP 85 to obtain ΘD.

Chapter 5: Dialogs in CASTEP
The following topics describe the dialogs in CASTEP:
CASTEP Calculation dialog
CASTEP Analysis dialog
Use the Save settings... option to save the current dialog settings.
CASTEP Calculation dialog

The Calculation dialog allows you to set up and run a CASTEP calculation.
It contains the following tabs:
Setup: Allows you to choose the type and quality of calculation that CASTEP will perform, along with
other basic input options, including exchange-correlation functional, spin polarization, and total
charge.
Electronic: Allows you to set the parameters associated with the electronic Hamiltonian. These
include the basis set, pseudopotentials, SCF convergence criteria, and integration accuracy.
Properties: Allows you to select the properties that will be computed as part of a CASTEP calculation.
These include electronic properties (such as band structure, density of states, and population
analysis), optical properties, vibrational properties, and stress.
Job Control: Allows you to specify settings for the CASTEP job.
Run: Runs a job using the settings specified. The results are placed in a subfolder of the current
Materials Studio project directory.
Note: This button is enabled only when the current 3D model document contains a periodic
structure.
Run | Copy Script: Converts the current settings to a script and copies the script to the clipboard. Refer
to the Generating scripts topic for more information on using sections of scripts generated from a
dialog.
Files...: Provides access to the CASTEP Job Files dialog which allows you to save input files for a CASTEP
calculation without running the job, or to run a job using an existing set of input files.
This functionality is provided for users who need to run the CASTEP server program in standalone mode,
or who wish to edit the CASTEP input files in order to gain access to features not supported by the
CASTEP interface.
Help: Displays the Help topic for the current tab.
Access methods
Menu Modules | CASTEP | Calculation

Toolbar | Calculation
Setup tab
The Setup tab allows you to choose the type and quality of calculation that CASTEP will perform along
with other basic input options such as exchange-correlation functional, spin polarization, and total
charge.

Task: Select the type of calculation that CASTEP will perform from the dropdown list. Available options
are:
Energy - performs a single-point energy calculation
Geometry Optimization - searches for a minimum energy structure
Dynamics - performs a molecular dynamics calculation
Elastic Constants - performs an elastic constants calculation
TS Search - performs a transition state search
TS Confirmation - produces a refined reaction path based on a TS search
Properties - calculates properties based on the results obtained from one of the other tasks
More...: Provides access to further options for the selected task: opening the CASTEP Geometry
Optimization, CASTEP Dynamics, CASTEP Elastic Constants, CASTEP Transition State Search , or CASTEP
TS Confirmation dialogs.
Quality: Set the overall quality of a single-point energy, geometry optimization, or dynamics calculation.
This quality affects the basis set, k-point, and SCF convergence criteria, along with the convergence
criteria for the Geometry Optimization, Elastic Constants, and TS Search tasks. Available options are:
Express
Coarse
Medium
Fine
Ultra-fine
Tip: Use the Coarse quality setting for a quick assessment of the calculation. Use the Express quality
setting to achieve a good compromise between speed and accuracy which is appropriate for most
calculations. Use Fine and Ultra-fine quality settings for calculations that require very high accuracy, at
the expense of longer calculation times. Carry out convergence testing for highly sensitive calculations
by increasing the quality setting and possibly by increasing accuracy of the basis set and the k-point
sampling.
The Quality setting affects all relevant task parameters that control the precision of the simulation. If
any parameter is set to a value different from that specified by the overall quality level, the Quality is
displayed as Customized.
Functional: Select the type of DFT exchange-correlation potential to be used in the calculation. Choose
the class of functional from the first dropdown list, then select the specific functional from the second
dropdown list.

LDA: local functional

CA-PZ: Ceperley and Alder, 1980; data as parameterized by Perdew and Zunger, 1981
GGA: gradient-corrected functionals
PBE: Perdew et al., 1996
RPBE: Hammer et al., 1999
PW91: Perdew et al., 1992
WC: Wu and Cohen, 2006
PBESOL: Perdew et al., 2008
BLYP: exchange from Becke, 1988; correlation from Lee, Yang, Parr, 1988
m-GGA: meta-GGA functional
RSCAN: Bartók and Yates, 2019; regularized version of the SCAN functional by Sun et al., 2016
Nonlocal: Nonlocal functionals
HF
HF-LDA
sX
sX-LDA
Hybrid: Hybrid functionals
PBE0
B3LYP
HSE03
HSE06
Notes:
Meta-GGA functional is not compatible with DFT-D corrections, spin-orbit coupling, J-coupling ,
linear-response phonons, or polarizability calculations. The formalism cannot be used with
mixture atoms. Only on the fly generated pseudopotentials can be used.
Nonlocal and Hybrid functionals can only be used for insulators using All Bands/EDFT Electronic
minimizer for Energy and Geometry Optimization (without cell optimization) tasks. It is not
compatible with stress, NMR, phonon, or polarizability calculations. The formalism cannot be
used with mixture atoms and only norm conserving potentials can be used. Note that stress
calculations, and hence cell optimization and the Elastic Constants task, are supported for
screened exchange versions, sX and sX-LDA.
There is an important difference between standard DFT calculations with local exchange-
depends on the wavefunctions at SCF k-points, while in the former case, the potential depends
only on electron density. This difference can make calculations a lot more expensive in terms of
memory usage and CPU time, so it is advisable to limit the number of SCF k-points that you use in
such situations. This is particularly relevant for small unit cells, where the default settings may
generate a very large k-point set.
Use method for DFT-D correction: When checked, the selected method will be used for dispersion
corrections. Available options are:

TS for GGA PBE, PBESOL, RPBE, BLYP, PW91; also for PBE0 and B3LYP
Grimme for GGA PBE, GGA BLYP, and B3LYP
OBS for GGA PW91 and LDA
MBD* for GGA PBE; also for HSE03, HSE06, and PBE0
Note: The option selected will automatically update the Use custom DFT-D parameters setting on the
DFT-D tab of the CASTEP Electronic Options dialog.
Spin polarization: Select how spin density should be treated. Available options are:
Non-polarized also known as 'spin-restricted' calculation, uses the same orbitals for alpha and beta
spins.
Collinear also known as 'spin-unrestricted' calculation, separate calculation for majority and minority
spin projections.
Non-collinear the calculation allows spin density to vary the quantization axis in each point of space.
Use formal spin as initial: When checked, indicates that the initial value for the number of unpaired
electrons for each atom will be taken from the formal spin specified for each atom. This starting value
will be subsequently optimized during the calculation. If unchecked, the initial value for the number of
unpaired electrons can be specified. Default = checked.
Note: This option is enabled only if the Spin polarization is Non-collinear or Collinear.
Note: Atom-resolved initial spin is used only if the Electronic minimizer is set to Density mixing on the
SCF tab of the CASTEP Electronic Options dialog or if the DFT+U is selected.
Use DFT+U: When checked, indicates that DFT+U will be used (also known as the LDA+U formalism).
Actual values of U can be set up through the Hubbard U tab of the Electronic Configuration dialog.
Note: This option is only enabled if the Spin polarization is Collinear.
Note: The DFT+U formalism is not compatible with NMR or polarizability calculations. The formalism
cannot be used with mixture atoms or real-space pseudopotentials.
Include spin-orbit coupling: When checked, indicates that spin-orbit coupling will be added to the
Hamiltonian.

Note: This option is only enabled if the Spin polarization is Non-polarized or Collinear. The formalism
is currently implemented only for tabulated norm-conserving pseudopotentials, with no LDA+U
corrections, and is not supported for nonlocal exchange-correlation functionals. Additionally, it is not
yet compatible with calculations of:
NMR
Dipole corrections
Linear response, including polarizability calculation
Optical properties
Electronic excitations
Partial density of states
Hirshfeld population analysis
Visualization of the electrostatic potential is also not yet implemented.
Metal: When checked this indicates that the system is metallic so that empty bands can be created and
edited. When unchecked the Fix occupancy checkbox on the SCF tab of the CASTEP Electronic Options
dialog is checked. When unchecked the k-point separations used by default are coarser. Default =
checked.
Note: In some calculations is not sufficient to use fixed orbital occupancies if the system under
investigation should actually have a band gap according to DFT results. This applies to calculations
that use the linear response formalism for vibrational properties and to calculations of electric field
responses (polarizability and IR and Raman spectra). Attempting to study a metallic systems using
fixed orbital occupancies will result in poor convergence and usually in unphysical results for IR and
Raman intensities and for polarizability. If this is the case, check whether your system is metallic by
running either density of states or band structure calculations.
Charge: Specify the total charge on the unit cell.
Access methods
Menu Modules | CASTEP | Calculation | Setup

Toolbar | Calculation | Setup
CASTEP Geometry Optimization dialog

The Geometry Optimization dialog allows you to set up and display the parameters that control the
Geometry Optimization task.
Minimizer: Provides access to the parameters that specify the convergence level of the minimization
and the external pressure and allows you to control cell optimization.
Options: Provides access to the parameters that control the minimization algorithm.
Stress: Provides access to the parameters that control the external stress or hydrostatic pressure on
the structure.

Access methods

| More...
Toolbar | Calculation | Setup | More...
Minimizer tab
The Minimizer tab allows you to specify the convergence level of the minimization and the external
pressure, and to control cell optimization.
Quality: Set the geometry optimization convergence thresholds for energy change, maximum force,
maximum stress, and maximum displacement between optimization cycles. The optimization will stop
when all of these criteria are satisfied.
Four sets of convergence thresholds are available:
Coarse
Medium
Fine
Ultra-fine
The values of the convergence thresholds in each set are given in the table below:
Value Coarse Medium Fine Ultra-fine

Energy (eV/atom) 5 × 10-5 2 × 10-5 1 × 10-5 5 × 10-6
Max. force (eV/Å) 0.1 0.05 0.03 0.01
Max. stress (GPa) 0.2 0.1 0.05 0.02
Max. displacement (Å) 0.005 0.002 0.001 5 × 10-4
Alternatively, thresholds can be specified independently for Energy, Max. force, Max. stress, and Max.
displacement. If you enter your own values for any of these settings, the Quality is displayed as
Customized on both the Minimizer tab and the Setup tab of the CASTEP Calculation dialog.
Note: When the main quality is set to Express the geometry optimization quality is also set to
Express. In this case energy tolerance will be displayed in eV/cell rather than eV/atom, the default
value is 0.001 eV/cell. All other tolerances are ignored and geometry optimization runs stop when the
energy change is less than the tolerance regardless of the values of forces or displacements.
Energy: Specify the convergence threshold for the maximum energy change, in eV/atom, during the
geometry optimization. The units are eV/cell if the Quality is set to Express.
Max. force: Specify the convergence threshold for the maximum force, in eV/Å, during the geometry
optimization. If the Quality is set to Express, this tolerance by default will be set to a very high value and
will effectively be ignored in the calculation.
Max. stress: Specify the convergence threshold for the maximum stress, in GPa, during the geometry
optimization. If the Quality is set to Express, this tolerance by default will be set to a very high value and
will effectively be ignored in the calculation.

Max. displacement: Specify the convergence threshold for the maximum displacement, in Å, during the
geometry optimization. If the Quality is set to Express, this tolerance by default will be set to a very high
value and will effectively be ignored in the calculation.
Max. iterations: Specify the maximum number of geometry optimization cycles. If this number of cycles
is reached, then the calculation will stop, even if the convergence criteria are not satisfied.
Cell optimization: Specify whether the cell should be optimized and how. Default = None. Options are:
None - No cell optimization is requested and the Basis set for variable cell and Compressibility
options are not available.
Full - Complete optimization of the cell.
Fixed Volume - The cell is optimized while keeping the volume fixed, cell angles and cell lengths are
varied.
Fixed Shape - The cell is optimized while keeping the cell angles and cell length ratios fixed, the cell
volume is varied.
Basis set for variable cell: Specify the desired behavior of the basis set when the cell size changes.
Default = Fixed Basis Quality. Options are:
Fixed Basis Quality - The number of plane waves changes to maintain the fixed cutoff energy (finite
basis set correction is required)
Fixed Basis Size - The number of plane waves is kept constant, so the effective cutoff energy changes
(finite basis set correction is not required)
Tip: Fixed Basis Quality is the recommended option.
Compressibility: Specify an estimated compressibility value for the crystal under investigation in order
to accelerate the geometry optimization. Each entry in the dropdown list is interpreted as a preset
value:
Soft - 25 GPa, suitable for soft materials like molecular crystals
Medium - 200 GPa, suitable for most transition metals
Hard (default) - 500 GPa, suitable for minerals, ceramics, and hard metals
Note: CASTEP geometry optimization will respect constraints on the fractional coordinates of atoms.
These constraints may be imposed using the controls on the Atom tab of the Edit Constraints dialog.
Nonlinear constraints are respected only for P1 structures that do not contain mixture atoms and
only when the delocalized internals optimizer is used, that is, the Use delocalized internals checkbox
is checked on the Options tab of the CASTEP Geometry Optimization dialog.
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| More... | Minimizer
Toolbar | Calculation | Setup | More... |
Minimizer
Options tab
The Options tab allows you to specify the minimization algorithm and the parameters controlling the
algorithm.

Algorithm: Specify the minimization algorithm. These algorithms are supported by CASTEP:
LBFGS
BFGS
Damped MD
TPSD
The LBFGS algorithm is generally recommended, especially for large systems. It implements a universal
sparse preconditioner that accelerates geometry optimization (Packwood et al., 2016). However, if there
are constraints TPSD might be a better choice (see the Geometry optimization theory topic for further
details).
interface plane).
Note: The Damped MD algorithm is not used when cell optimization is performed.
Use line search: When checked, indicates that optimization should use the advanced line search
algorithm.
Note: This checkbox is checked by default, except when the main quality is set to Express. If you
specify the Express quality setting and then request line search, the Quality is displayed as
Customized on both the Minimizer tab and the Setup tab of the CASTEP Calculation dialog. In the
latter scenario, you must set convergence criteria for gradients and displacements to sensible values,
as the line search algorithm cannot function using only the energy change criterion.
Use delocalized internals: When checked, indicates that delocalized internal coordinates should be
used during geometry optimization, instead of Cartesian coordinates. This setting typically speeds up
the calculation by 2-3 times.
Note: The Use delocalized internals option is enabled only if the BFGS algorithm is selected.
Note: The delocalized internals minimizer does not currently support cell optimization. As a result,
CASTEP will automatically switch over to Cartesian coordinates when the cell is allowed to vary.
The delocalized internals minimizer respects nonlinear constraints only for P1 structures that do not
contain mixture atoms.
Damping algorithm: Specify the algorithm for the Damped MD method. The supported algorithms are:
Independent - the damping constant is chosen independently for each mode, so that all modes lose
energy at the same rate.
Coupled - the same damping constant is used for all modes at each step.
Steepest Descent
The Independent damping algorithm is recommended (see the Geometry optimization theory topic for
details).
Damping coefficient recalculation frequency: During the damped MD optimization, the damping
coefficients are recalculated occasionally to improve the damping rate. This value specifies the number
of MD steps between these recalculations.

Note: The Damping coefficient recalculation frequency value is not used by the steepest descent
algorithm.
Wavefunction extrapolation: Specify the method to be used for wavefunction extrapolation between
MD steps.
None - no extrapolation is performed.
1st VV - first-order extrapolation with variable coefficients.
2nd VV - second-order extrapolation with variable coefficients.
2/1 VV - alternate second- and first-order extrapolation with variable coefficients.
1st CC - first-order extrapolation with constant coefficients.
2nd CC - second-order extrapolation with constant coefficients.
2/1 CC - alternate second- and first-order extrapolation with constant coefficients.
Time step: Specify the time step to be used in the damped MD geometry optimization.
Auto-update time step: When checked, indicates that the time step will be automatically updated to
speed up the geometry optimization.
Note: The Time step and Auto-update time step controls are enabled only if the Damped MD
algorithm is selected.
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| More... | Options
Options
Stress tab
The Stress tab allows you to specify an external stress or hydrostatic pressure on the structure for
geometry optimization.
Note: The options on this tab are applicable only when cell optimization has been requested.
External stress: Specify any element of the external stress tensor on the structure, in GPa.
Equivalent hydrostatic pressure: Specify the hydrostatic pressure on the structure.
The hydrostatic pressure is one third of the trace of the stress tensor. When a value is specified here, the
diagonal elements of the stress tensor are modified so as to leave any anisotropic term unchanged.
Note: A positive value of external stress and hydrostatic pressure indicates that the structure is
compressed.
Reset external stress to zero: Sets all elements of the stress tensor to zero.
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| More... | Stress


Stress
CASTEP Dynamics dialog

The CASTEP Dynamics dialog allows you to set up and display the parameters that control the Dynamics
task.
Dynamics: Provides access to the main parameters that specify the dynamics, including choice of
ensemble, temperature, pressure, and the length of the run.
Options: Provides access to the parameters that control the details of the dynamics algorithm,
including thermostat, barostat and wavefunction extrapolation settings.
Stress: Provides access to the parameters that control the external stress or hydrostatic pressure on
the structure.
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| More...
Dynamics tab
The Dynamics tab allows you to specify the main parameters for controlling dynamics simulations.
Ensemble: Specify the ensemble to be used in the dynamics simulation.
NVE - dynamics at fixed volume and constant energy.
NVT - dynamics at fixed volume with a thermostat to maintain a constant temperature.
NPH - dynamics at constant enthalpy with a barostat to maintain a constant pressure.
NPT - dynamics with a thermostat to maintain a constant temperature and with a barostat to
maintain a constant pressure.
Initial velocities: Select the method of velocity initialization to be used for the dynamics calculation. The
available options are:
Random - set initial velocities to random value (default).
Current - set initial velocities to values currently defined on the structure.
Temperature: Specify the temperature of the dynamics simulation. For the NVE ensemble, the initial
random velocities of the atoms are scaled to this temperature.
Pressure: Specify the external pressure for the dynamics simulation in the NPH or NPT ensemble. For
Parrinello barostat full stress tensor can be specified on the Stress tab.
Time step: Specify the time step for the dynamics simulation.
Total simulation time: Specify the total time for the dynamics simulation. When modified the number
of steps is adjusted appropriately for the current time step.
Number of steps: Specify the total number of steps for the dynamics simulation.
Basis set for variable cell: Specify the desired behavior of the basis set when the cell size changes.

Fixed Basis Quality - the number of plane waves changes to maintain the fixed cutoff energy (finite
basis set correction is required).
Fixed Basis Size - the number of plane waves is kept constant, so the effective cutoff energy changes
(finite basis set correction is not required).
Tip: Fixed Basis Quality is the recommended option.
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| More... | Dynamics
Dynamics
Options tab
The Options tab allows you to specify parameters which control the details of the dynamics algorithm.
Thermostat: Specify the thermostat to be used for NVT or NPT dynamics. Available options are:
Langevin
Nose
NHL
Note: This option in enabled only if the NVT or NPT ensemble is selected on the Dynamics tab. The
Nosé-Hoover-Langevin (NHL) thermostat is only available for the NVT ensemble.
Barostat: Specify the barostat to be used for NPH or NPT dynamics. Available options are:
Andersen - scales the cell uniformly
Parrinello - allows variation in the cell shape
Note: This option in enabled only if the NPT or NPH ensemble is selected on the Dynamics tab.
Langevin constant: Specify the damping time of temperature fluctuations during Langevin NVT
dynamics. This time should normally be larger than the time scale of any motions of interest.
Nose Q ratio: Specify a scaling factor for the fictitious mass Q of the Nosé thermostat for Nosé or Nosé-
Hoover-Langevin NVT dynamics. A larger Q ratio implies increased damping of temperature fluctuations.
Cell time constant: Specify the characteristic cell time, which is used to estimate the mass associated
with the barostat. A larger value implies increased damping of pressure fluctuations.
Wavefunction extrapolation scheme: Specify the method to be used for wavefunction extrapolation
between molecular dynamics steps. This selection is not available when Use Extended Lagrangian (XL-
BOMD) is selected.

None - no extrapolation is performed.

1st VV - 1st order extrapolation with variable coefficients.
2nd VV - 2nd order extrapolation with variable coefficients.
2/1 VV - Alternate 2nd and 1st order extrapolation with variable coefficients.
1st CC - 1st order extrapolation with constant coefficients.
2nd CC - 2nd order extrapolation with constant coefficients.
2/1 CC - Alternate 2nd and 1st order extrapolation with constant coefficients.
Use eXtended Lagrangian (XL-BOMD): When checked, indicates that the extended Lagrangian
molecular dynamics (Steneteg 2010, Niklasson 2011) is used instead of the wavefunction extrapolation
schemes. The extended Lagrangian formulation allows significantly higher time step values to be used,
while conserving the constant of motion. This option is available only for fixed-cell (NVE and NVT)
ensembles. Default = checked.
Fix center of mass: When checked, indicates that the center of mass will be fixed during the dynamics
simulation. Default = unchecked.
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| More... | Options
Options
Stress tab
The Stress tab allows you to specify an external stress or hydrostatic pressure on the structure for
molecular dynamics.
Note: The options on this tab are available only when the NPT or NPH ensemble is selected on the
Dynamics tab.
External stress: Specify any element of the external stress tensor on the structure, in GPa.
Equivalent hydrostatic pressure: Specify the hydrostatic pressure on the structure.
The hydrostatic pressure is one third of the trace of the stress tensor. When a value is specified here, the
diagonal elements of the stress tensor are modified so that any anisotropic term remains unchanged.
Note: A positive value of external stress and hydrostatic pressure indicates that the structure is
compressed.
Note: When the Andersen barostat is selected on the Options tab only hydrostatic pressure is used
by CASTEP.
Reset external stress to zero: Sets all elements of the stress tensor to zero.
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| More... | Stress


Stress
CASTEP Elastic Constants dialog

The CASTEP Elastic Constants dialog is accessed from the More... button on the Setup tab, when the
Elastic Constants option is selected from the Task dropdown list.
Elastic Constants: Allows you to specify the strains applied to the crystal, used for calculating elastic
constants.
Options: Allows you to set the convergence level of the elastic constants calculation.
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| More...
Elastic Constants tab

The Elastic Constants tab allows you to set parameters that define how the elastic constants will be
calculated.
Number of steps for each strain: Specify the number of distorted structures generated for each strain
pattern. An odd value implies that the undistorted structure will be among those generated. Even
values are, therefore, recommended.
Maximum strain amplitude: Set the maximum distortion used. Values in excess of 0.01 are not
recommended, since the crystal is likely to be beyond linear elasticity. However, values of 0.001 and
below will generate a set of structures that are very similar to one another. In these circumstances,
computational noise may become significant when comparing the calculated stress values for similar
structures.
Use volume-conserving strains: When checked indicates that the strain patterns will be modified to use
volume-conserving strains, when possible. This option should only be used if the standard set of strains
is producing unsatisfactory results.
Strain pattern: Displays a matrix showing the nonzero components of the strain tensor for each
generated strain. For example, the line:
1 0 0 1 0 0
means that the xx, yz (and zy) components of the strain tensor will be non-zero.
Note: This matrix is not editable.
Note: For trigonal symmetry, the orientation standard where C lies along the z-axis and A is in the xz
plane must be used. For further details on the lattice orientation standard and how to set it, see the
Viewing or changing the lattice parameters topic.

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| More... | Elastic Constants
Elastic Constants
Options tab
The Options tab allows you to specify the convergence level of the elastic constants calculation.
Quality: Sets the convergence thresholds for energy change, maximum force, and maximum
displacement between cycles. This is used for the geometry optimization runs that are required for the
elastic constants calculation. The calculation will stop when all of these criteria are satisfied.
Four sets of convergence thresholds are available; Coarse, Medium, Fine and Ultra-fine. The values of
each convergence threshold in each set are given in the table below:
Quality Energy (eV/atom) Force (eV/Å) Displacement (Å)

Coarse 1 × 10-5 0.02 0.001
Medium 4 × 10-6 0.01 4 × 10-4
Fine 2 × 10-6 0.006 2 × 10-4
Ultra-fine 1 × 10-6 0.002 1 × 10-4
Customized User defined User defined User defined
Alternatively, thresholds can be specified independently. If user defined values are used, the Quality
displayed is Customized.
Note: When the main quality is set to Express the elastic constants quality is also set to Express. In
this case energy tolerance will be displayed in eV/cell rather than eV/atom, the default value is
0.001 eV/cell. All other tolerances are ignored and geometry optimization runs stop when the energy
change is less than the tolerance regardless of the values of forces or displacements.
Energy: Specify the convergence threshold for the maximum energy change, in eV/atom. The units are
eV/cell if the Quality is set to Express.
Max. force: Specify the convergence threshold for the maximum force, in eV/Å. If the Quality is set to
Express, this tolerance by default will be set to a very high value and will effectively be ignored in the
calculation.
Max. displacement: Specify the convergence threshold for the maximum displacement, in Å. If the
Quality is set to Express, this tolerance by default will be set to a very high value and will effectively be
ignored in the calculation.
Max. iterations: Specify the maximum number of elastic constants cycles. If this number of cycles is
reached, then the calculation will stop even if the convergence criteria are not satisfied.

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| More... | Options
Options
CASTEP Transition State Search dialog

The CASTEP Transition State Search dialog allows you to set up and display the parameters that control
the TS Search task, including the protocol to be used and the quality of the search.
Note: CASTEP transition-state searches require a trajectory document (for example, an .arc or
.xtd file) as input. You will not be able to start a transition-state search run unless a suitable
document is in scope.
Note: When a transition state search is performed on a periodic system the unit cell is fixed.
Search protocol: Select the type of synchronous transit that will be performed from the dropdown list.
Available options are:
LST Maximum - performs a single linear synchronous transit (LST) maximization, bracketing the
maximum between the reactants and product
Halgren-Lipscomb - performs an LST maximization, followed by a single-line search minimization
LST/Optimization - performs an LST maximization, followed by a full conjugate gradient minimization
Complete LST/QST - performs an LST, followed by repeated conjugate gradient minimizations and
quadratic synchronous transit (QST) maximizations until a transition state has been located
QST/Optimization - starting from a QST, performs repeated maximizations and conjugate gradient
minimizations until a transition state has been located
Quality: Set the TS search convergence thresholds for the root mean square (RMS) forces on the atoms.
The search will stop when this criterion is satisfied.
Five quality settings are available:
Express
Coarse
Medium
Fine
Ultra-fine
The value of the convergence threshold for each setting is given in the table below:
Express Coarse Medium Fine Ultra-fine

RMS convergence (eV Å-1) 0.1 0.5 0.25 0.05 0.01
RMS convergence: Specify the value, in eV Å-1, at which convergence is considered to take place in terms
of the RMS of the gradients.
Max. number QST steps: Specify the maximum number of QST maximization cycles. If this number of
cycles is reached, then the calculation will stop, even if the convergence criteria are not satisfied.

Optimize reactants and products: Specifies that the input structure for the reactant and product in a TS
search calculation should be optimized to a local minimum. Selecting this allows the TS search to start
from a "raw" trajectory, where the reactant and product structures have not already been optimized.
Note: This choice may lead to reactant and product structures deviating substantially from the input
structures, so it is recommended that you carefully check the final path.
Calculate partition functions: Specifies whether to calculate partition functions based on the Gamma-
point dynamical matrix for the reactants, products, and the transition state. This data will be stored in
the output 3D Atomistic Collection document.
Note: This is not available unless Optimize reactants and products is checked.
Help: Displays the Help topic in a browser.
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| More...
CASTEP TS Confirmation dialog

The CASTEP TS Confirmation dialog allows you to set up and display the parameters that control the
simulation in a CASTEP TS Confirmation task.
Quality: Set the geometry optimization convergence thresholds for energy change, maximum force, and
maximum displacement between optimization cycles. The optimization will stop when the energy
convergence is satisfied along with either the displacement or gradient criteria.
Four sets of convergence thresholds are available:
Coarse
Medium
Fine
Ultra-fine
The values of the convergence thresholds in each set are given in the table below:
Value Coarse Medium Fine Ultra-fine

Energy (eV/atom) 1 × 10-4 2 × 10-5 1 × 10-5 5 × 10-6
Max. force (eV/Å) 0.5 0.1 0.05 0.02
Max. displacement (Å) 0.05 0.005 0.004 0.003
Alternatively, thresholds can be specified independently for Energy, Max. force, and Max.
displacement. If you enter your own values for any of these settings, the Quality is displayed as
Customized on both the CASTEP TS Confirmation dialog and the Setup tab of the CASTEP Calculation
dialog.

Note: When the main quality is set to Express the transition state confirmation quality is also set to
Express. In this case the energy tolerance will be displayed in eV/cell rather than eV/atom, the default
value is 0.002 eV/cell.
Energy: Specify the convergence threshold for the maximum energy change, in eV/atom, during the
geometry optimization. The units are eV/cell if the Quality is set to Express.
Max. force: Specify the convergence threshold for the maximum force, in eV/Å, during the geometry
optimization.
Max. displacement: Specify the convergence threshold for the maximum displacement, in Å, during the
geometry optimization.
Altering the value of any threshold is allowed and results in the Quality being set to Customized.
Max. images: The number of intermediate NEB images used during the transition state confirmation.
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| More...
Electronic tab
The Electronic tab allows you to set the parameters associated with the electronic Hamiltonian. These
include the basis set, pseudopotentials, SCF convergence criteria, and k-point set.
Energy cutoff: Select the precision used for the plane wave basis set.
Coarse
Medium
Fine
Ultra-fine
The actual value of the energy cutoff corresponding to the selected quality for the current structure is
also displayed.
Note: Calculation of the NMR parameters may require the Energy cutoff to be set to a higher value
than for total energy or geometry optimization calculations. It is advisable to study the convergence
of the results as the Energy cutoff parameter is increased. Generally, setting the cutoff to between
270 and 400 eV should produce convergence of the shielding constant to about 1 ppm, but in some
cases, the cutoff has to be increased up to 550 eV.
SCF tolerance: Select the threshold used to determine whether an SCF has converged. Available options
and associated convergence thresholds are:
Coarse - 10-5 eV/atom
Medium - 2 × 10-6 eV/atom
Fine - 10-6 eV/atom
Ultra-fine - 5 × 10-7 eV/atom

Note: When the main quality is set to Express the SCF tolerance is also set to Express which
corresponds to 10-4 eV/cell.
Energy tolerances per: Specifies whether energy tolerances are calculated as the energy change per
atom (Atom is the default setting) or per unit cell (the Cell value is enforced when the main quality, and
hence the SCF tolerance quality, is set to Express).
k-point set: Define the number of integration points that will be used to integrate the wavefunction in
reciprocal space. Available options are:
Gamma - a single point at (0, 0, 0)
Coarse
Medium
Fine
Pseudopotentials: Select the type of pseudopotential to be used. Two different types of
pseudopotentials are available, ultrasoft and norm-conserving; both of them are available as either
generated on the fly (OTFG) potentials or as tabulated potentials. OTFG potentials are generally
preferred for reasons of accuracy and consistency. They are required for NMR calculations.
OTFG ultrasoft (default) - the preferred option, ultrasoft pseudopotentials allow calculations to be
performed with lower energy cutoffs. On-the-fly generation produces potentials that are consistent
between solid state and pseudo-atom calculations since they use the same exchange-correlation
functional throughout. The set of OTFG ultrasoft pseudopotentials introduced in Materials Studio
8.0 provides results in close agreement with all electron calculations and is very accurate for
describing ground state structures.
OTFG norm conserving - typically harder and therefore more computationally expensive than
ultrasoft pseudopotentials. Norm-conserving potentials are currently required for linear response-
based calculations of phonon properties and of polarizabilities and for calculations with nonlocal
exchange-correlation functionals (for example, screened exchange).
Ultrasoft - tabulated ultrasoft pseudopotentials, provided for compatibility with earlier versions of
Materials Studio.
Norm conserving - tabulated norm-conserving pseudopotentials, provided for compatibility with
earlier versions of Materials Studio.
Note: When you specify the type of pseudopotential to be used in this way, the default
pseudopotential of that type for each element will be used in the calculation.
Tip: Use the Electronic Options dialog to exercise more control over which pseudopotentials are used
for each element.
Relativistic treatment: The way relativistic effects are incorporated into OTFG pseudopotentials.
Options are:
Schroedinger
Koelling-Harmon (default)
ZORA

Use core hole: Specify whether to include core holes in the calculation; core holes can be used in core
level spectroscopy calculations and should be defined using the Core Hole tab of the Electronic
Configuration dialog.
Note: For calculations exploiting core holes, on-the-fly pseudopotentials must be used.
If the Use core hole checkbox is not checked, any core holes in the input system will not be preserved
during the calculation.
the charge of 0.5).
More...: Provides access to the CASTEP Electronic Options dialog, which allows you to set up and display
further details of the electronic Hamiltonian.
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Menu Modules | CASTEP | Calculation |

Electronic
Toolbar | Calculation | Electronic
CASTEP Electronic Options dialog

The CASTEP Electronic Options dialog allows you to set up and display the details of the electronic
Hamiltonian used in CASTEP calculations. These parameters are relevant for the Energy, Geometry
Optimization, Dynamics, Elastic Constants and TS Search tasks.
Basis : Provides access to the plane-wave energy cutoff, FFT grid specification, and finite basis set
correction.
SCF: Provides access to the parameters that control the electronic minimization algorithm.
k-points: Provides more detailed access to the k-point set.
Potentials: Provides control over which pseudopotentials will be used for each element in the
structure.
DFT-D: Provides access to the parameters for van der Waals dispersion correction calculations.
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Electronic | More...
Toolbar | Calculation | Electronic |
More...

Basis tab
The Basis tab provides access to basis set information, including the plane-wave energy cutoff, FFT grid
specification and finite basis set correction.
Use custom energy cutoff: When checked, a custom value for the energy cutoff can be specified in the
adjacent text box. Otherwise the text box displays the energy cutoff appropriate for the Energy cutoff
quality parameter on selected on the Electronic tab.
Density: Specify the quality of the FFT grid. Three options are available:
Standard
Fine
Precise
The FFT grid parameters are chosen such that they provide a good representation of the electron
density. At the Precise level, an exact representation of the density is provided for the given energy-
cutoff. At the Standard and Fine levels, a reduced FFT grid is used to speed up the calculation. Some
aliasing will occur as a result but the effect on the SCF solution is usually small. The FFT grid parameters
that will be used in the CASTEP calculation are displayed as derived using the current energy-cutoff and
unit cell parameters.
Augmentation density scaling factor: Specify a finer grid for representation of the augmentation charge
density in the atomic core region. By default the same grid is used as for the standard electron density; it
is reasonable in some cases to increase the augmentation grid by a factor of up to 4 in order to improve
the accuracy of calculations. This can be controlled by the Quality setting on the Setup tab of the
CASTEP Calculation dialog.
Apply finite basis set correction: Specify when to use a finite basis set correction in the evaluation of
energy and stress. This can be controlled by the Quality setting on the Setup tab of the CASTEP
Calculation dialog.
This correction gives a volume dependent addition to the energy that may result in a significant
correction to any calculated stress. It is particularly important where an accurate stress or cell geometry
optimization is required. Three settings are available:
Smart - apply the correction only when stress is required. This will include any cell geometry
optimization.
Always - apply the correction to all calculations.
Never - do not apply a correction, even when stress is calculated. Any result for stress or cell
geometry may be unreliable as a result.
Correction mode: Specify how the finite basis set correction should be calculated. The evaluation of the
correction requires an estimate for the derivative of the total energy with respect to the logarithm of the
plane-wave energy cutoff. The options are:
Automatic - the energy derivative will be calculated automatically using numerical differentiation.
Manual - the energy derivative is specified manually.
Numerical differentiation using: Specify the number of energy points to use in evaluating the energy
derivative required for the finite basis set correction. A converged SCF energy will be evaluated at each
point.
Note: This option is enabled only if the Automatic Correction mode is selected.
Energy derivative w.r.t. cutoff: Specify the value of the energy derivative required for the finite basis set
correction.

Note: This option is enabled only if the Manual Correction mode is selected.
Access methods

Electronic | More... | Basis
More... | Basis
SCF tab
The SCF tab on the CASTEP Electronic Options dialog provides access to parameters that control the
electronic minimization algorithm.
SCF tolerance: Specify the SCF convergence threshold. This will override the SCF tolerance option
specified on the Electronic tab.
Note: When calculating linear response properties (for example phonons, polarizabilities, NMR
properties), it is important that the SCF convergence threshold is sufficiently strict from the
computational point of view to accurately calculate these properties. When the calculation of linear
response properties is requested, CASTEP will use a convergence threshold of 10-8 eV atom-1, unless
the specified threshold is lower. To force CASTEP to use a less stringent threshold, the ELEC_ENERGY_
TOL parameter should be manually inserted in the input parameters (.param) file for the property
calculation.
Max. SCF cycles: Set the maximum number of SCF iterations allowed for an energy calculation. The
energy calculation will end after the specified number of iterations, even if the SCF has not converged.
Convergence window: The convergence tolerance window for SCF. This is number of SCF iterations in a
row for which convergence criteria are fulfilled. This parameter is required in order to avoid occasional
oscillations.
Electronic minimizer: Specify the electronic minimization method to be used for the SCF calculation.
Two options are available, Density Mixing and All Bands/EDFT.
Tip: The Density Mixing option is recommended, particularly for variable occupancy calculations. The
All Bands/EDFT method is usually slower and requires more memory. However, the EDFT scheme is
recommended for metallic systems where converging electronic structure using Density Mixing
option proves problematic.
Charge: Specify the amplitude for charge density mixing (that is, the amplitude of the output charge
density to mix with the input charge density to obtain input for the next iteration).
Note: This option is enabled only if the Density Mixing minimization method is selected.
Spin: Specify the amplitude for spin density mixing, that is, the amplitude of the output spin density to
mix with the input spin density to obtain input for the next iteration.
Note: This option in enabled only for spin-polarized calculations using the Density Mixing
minimization method.
More...: Provides access to the CASTEP Density Mixing Options dialog, where more detailed control over
the Density Mixing electronic minimization method is available.

Note: This option is enabled only if the Density Mixing minimization method is selected.
Fix occupancy: When checked, the electronic occupation numbers will be fixed during electronic
minimization. Only the lowest, occupied states will be included in the calculation. Default = checked.
More...: Provides access to the CASTEP Occupancy Options dialog, where more detailed control over the
occupancies is available.
Apply dipole corrections: Select the type of dipole corrections to apply from the dropdown list.
None (default)
Non self-consistent
Self-consistent
Self-consistent is the most accurate option, as this affects the electrostatic potential as well as the total
energy and its gradients. This is the only option that is suitable to investigate the effect of dipole
corrections, for example on surface workfunctions.
Tip: It is recommended to use the All Bands/EDFT electronic minimization scheme when applying a
self-consistent dipole correction to an elongated cell of a slab representing a metal surface; the
Density mixing minimization scheme may fail to converge for such systems.
Non self-consistent is recommended for cases where it is hard to converge the SCF with Apply dipole
corrections set. This option can only be used for Energy calculations and is not compatible with phonon
calculations.
Note: Dipole corrections will be applied only if the system is either molecule in the box or a periodic
slab with the vacuum layer of at least 8 Å.
Note: If dipole corrections are to be applied the symmetry of the system will be converted to P1 to
bring the molecule (or slab) into the center of the unit cell.
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Electronic | More... | SCF
More... | SCF
CASTEP Density Mixing Options dialog

The CASTEP Density Mixing Options dialog allows you to specify the parameters that control the Density
Mixing method of electronic minimization.
Mixing scheme: Specify the method used for mixing the input densities and output densities from the
current iteration to obtain the input density for the next iteration in the iterative solution for the SCF.
The supported methods are:

Linear - the input density and the output density are mixed in a simple linear combination.
Kerker - the input density and output density are mixed using a reduced mixing factor for the long
length scale Fourier coefficients of the density.
Pulay (default) - the output density is mixed with densities from a number of previous iterations,
using the RMM-DIIS method, leading to more rapid convergence.
Broyden - the output density is mixed with densities from a number of previous iterations, using the
quasi-Newton relaxation method. The overall convergence is similar to that of Pulay mixing.
The Pulay or Broyden method is recommended. The Linear method is not usually suitable for large
systems.
Charge mixing amplitude: Specify the amplitude of the output charge density to mix with the input
charge density to obtain input for the next iteration.
Charge mixing cutoff: Specify the length scale used. Charge mixing is reduced for Fourier coefficients at
reciprocal lattice vectors less than about this value.
Note: This option is enabled only if the Kerker, Broyden, or Pulay density mixing method is selected.
DIIS history list: Specify the number of previous iterations to be considered in the DIIS for the Pulay or
Broyden density mixing method.
Note: This option is enabled only if the Pulay or Broyden density mixing method is selected.
Spin mixing amplitude: Specify the amplitude of the output spin density to mix with the input spin
density to obtain input for the next iteration.
Note: This option is enabled only for spin-polarized calculations.
Spin mixing cutoff: Specify the length scale used. Spin mixing is reduced for Fourier coefficients at
reciprocal lattice vectors less than about this value.
Note: This option is enabled only for spin-polarized calculations using the Kerker, Broyden, or Pulay
density mixing methods.
Access methods

Electronic | More... | SCF | More...
More... | SCF | More...
CASTEP Occupancy Options dialog

The CASTEP Occupancy Options dialog provides access to parameters that control occupancies in
CASTEP calculations.
By default, CASTEP calculations are performed with variable occupancy. The fixed occupancy option is
only suitable for structures that are known to be insulators or closed shell systems at the level of theory
used in the CASTEP calculation.
Empty bands: Specify the number of additional bands to be included in an electronic minimization as a
percentage of the number of occupied bands.

Note: This option is enabled only for variable occupancy calculations.

Smearing: Specify the broadening to be applied to the electronic occupation.
Note: This option is enabled only for variable occupancy calculations.
Optimize total spin after: Specify the number of SCF iterations for which the total electronic spin will
remain fixed before being allowed to vary.
Note: This option is enabled only for spin-polarized variable occupancy calculations.
Note: The spin will be fixed throughout the calculation (including possible steps of geometry
optimization) if the checkbox is unchecked.
Tip: In spin-polarized systems there may be more than one stable SCF solution with different total
spin values. By setting the initial spin on the Setup tab and by fixing the total spin value for a number
of SCF iterations, it is possible to exert some control over which solution is found.
Access methods

Electronic | More... | SCF | More...
More... | SCF | More...
k-points tab
The k-points tab provides access to more detailed options for controlling the k-point set used in CASTEP
calculations.
The Monkhorst-Pack k-point grid to be used in the calculation can be specified in several ways. For cubic
cells and for the C direction of hexagonal cells the even and odd grids for the Monkhorst-Pack scheme
give the same number of k-points. However, the even grid provides better sampling and will always be
used automatically under these conditions. This ensures that a good grid with k-point separation at (or
less than) the specified target can be achieved more economically. As a consequence, such lattices may
have much finer separations than requested as odd grids have been excluded - even though they would
have been closer to the specified separation - and the better even grids have been taken in preference.
Gamma point only: When selected, indicates that a single k-point at (0,0,0) will be used for the density
of states calculation.
Quality: When selected, indicates that the k-point grid will be generated using a k-point separation
appropriate to the specified quality level. Select the desired quality level from the dropdown list.
Coarse
Medium
Fine
The k-point separations associated with the three Quality settings depend on whether the Metal
checkbox on the Setup tab is checked and are as follows:

Quality k-point separation (Å-1)

Metal checked Metal unchecked
Coarse 0.07 0.1
Medium 0.05 0.08
Fine 0.04 0.07
Separation: When selected, indicates that the k-point grid will be generated according to the specified k-
point separation. Specify the k-point separation, in Å-1, in the associated text box.
Note: When the Separation option is selected, the Monkhorst-Pack parameters are derived to give
the specified separation between neighboring grid points.
Custom grid parameters: When selected, indicates that the k-point grid will be generated using the
Monkhorst-Pack grid parameters and the origin shift in fractional reciprocal space coordinates specified
in the Grid parameters and Origin shift text boxes, respectively.
Grid parameters: Specify the Monkhorst-Pack grid parameters in each of the lattice directions.
Actual spacing: Displays the k-point separation, in Å-1, resulting from the currently specified
Monkhorst-Pack grid parameters in each of the lattice directions.
Origin shift: Specify the offset of the Monkhorst-Pack grid in fractional reciprocal space coordinates.
Note: The Grid parameters and Origin shift controls are enabled only if the Custom grid parameters
option is selected.
Display points...: Displays the number and fractional coordinates of the reciprocal space mesh points
that would be generated using the currently specified parameters.
Note: The actual set of k-points that will be used in the calculations may be altered if the symmetry of
the system changes or DFT+U calculation is requested.
Access methods

Electronic | More... | k-points
More... | k-points
Potentials tab
The Potentials tab allows you to control which pseudopotentials will be used for each element in the
structure.
Scheme: Select the type of pseudopotential to be used. Two different types of pseudopotentials are
available, ultrasoft and norm-conserving; both of them are available as either generated on the fly
(OTFG) potentials or as tabulated potentials. OTFG potentials are generally preferred for the reasons of
accuracy, consistency, and finally these are required for NMR calculations:

OTFG ultrasoft (default) - the preferred option, ultrasoft pseudopotentials allow calculations to be
performed with lower energy cutoffs. On-the-fly generation produces potentials that are consistent
between solid state and pseudo-atom calculations since they use the same exchange-correlation
functional throughout. The set of OTFG ultrasoft pseudopotentials introduced in Materials Studio
8.0 provides results in close agreement with all electron calculations and is very accurate for
describing ground state structures.
OTFG norm conserving - typically harder and therefore more computationally expensive than
ultrasoft pseudopotentials. Norm-conserving potentials are currently required for linear response-
based calculations of phonon properties and of polarizabilities and for calculations with nonlocal
exchange-correlation functionals (for example, screened exchange).
Ultrasoft - tabulated ultrasoft pseudopotentials, provided for compatibility with earlier versions of
Materials Studio.
Norm conserving - tabulated norm-conserving pseudopotentials, provided for compatibility with
earlier versions of Materials Studio.
Note: The latest set of OTFG settings for ultrasoft pseudopotentials has been developed in order to
minimize the error with respect to fully converged all-electron DFT calculations. The error achieved by
this set is 0.4 meV/atom, which puts CASTEP among the most accurate pseudopotential codes
available. A full definition of the test framework and the meaning of the error is given by Lejaeghere et
al. (2014), and on the website of the Delta project: http://molmod.ugent.be/deltacodesdft. The files
that correspond to this set have the _2017R2 suffix . This is the recommended set of OTFG ultrasoft
potentials. Files with the _2017R2ncp suffix are recommended when norm-conserving potentials
are required (this set has a 1.1 meV/atom error in the Delta project tests). In addition, a set of "high
throughput" ultrasoft OTFG settings is available for scripting; this QC5 set generally requires lower
cutoff energy and offers faster but less accurate calculations (1.9 meV/atom error in the Delta project
tests).
Note: When you specify the type of pseudopotential to be used in this way, the default
pseudopotential of that type for each element will be used in the calculation.
Representation: Choose between Reciprocal space and Real space representations of the
pseudopotentials.
Tip: The real space representation may give a performance advantage for large systems.
More...: Provides access to the CASTEP Real Space Potentials dialog, which allows you to specify details
of the transformation of pseudopotentials to a real space representation.
Note: This button is enabled only if Real space is selected from the Representation dropdown list.
Selected potentials: Displays information about the selected pseudopotentials for each element in a
grid.
There is a row in the grid for each element. The element type, current pseudopotential, energy, and
valence (Z) are displayed. To select a different pseudopotential for a particular element, click in the
appropriate pseudopotential grid cell and choose a new pseudopotential from the dropdown list.
If changes are made to the default pseudopotentials, the Scheme displayed is Custom.

Show potentials for all elements: When checked, the Selected potentials list will display information
about all elements in the periodic table for which pseudopotentials are available. Otherwise, only
elements present in the current structure are displayed in the list. Default = unchecked.
View: Displays a modal view on the selected pseudopotential file.
External Potential
Electric field: Specify the external electric field strength, in eV/Å/e.
Field direction (X Y Z): Vector specifying the direction of the electric field.
Note: Only systems that contain molecules or slabs are appropriate for electric field calculations.
For slabs, the field must be along the surface normal. In both cases atoms should be positioned in the
middle of the cell and the symmetry must be P1.
Note: The field direction is specified in Cartesian coordinates. The values of the X, Y, and Z direction
components of the electric field are interrelated. The three field components are used to define a unit
vector. When a job is launched the direction components are normalized to give a unit vector which
is then multiplied by the field magnitude to give the actual field components. Entering a vector with
all zero components has the same effect as entering a (111) vector.
Access methods

Electronic | More... | Potentials
More... | Potentials
CASTEP Real Space Potentials dialog

The CASTEP Real Space Potentials dialog allows you to specify the parameters describing the
transformation of pseudopotentials to a real space representation.
Core radius: Specify the real space core radius of the element displayed. Change the element type using
the dropdown list.
Tip: Enter zero to reset the core radius for the displayed element to the default value.
Note: The real space core radius determines the radius of real space integration to be used in the
calculation. It should be larger than the core radius used in pseudopotential generation, normally by
a factor of 1.5 to 2.0, so as to overcome the aliasing problems inherent in the real space integration
method.
Reset all core radii to defaults: Sets all core radii to the default values.
Use custom energy cutoff for transformation: When checked, a value may be specified for the energy
cutoff used in the transformation to the real space form of pseudopotentials. Otherwise a value will be
calculated automatically based on the plane-wave energy cutoff to be used in the calculation. Default =
unchecked.
Impose tolerance: When checked, the real space pseudopotential transformation will be tested to
ensure it is of the quality specified in the dropdown list. Default = checked.

If the transformation is not of the requested quality, then the CASTEP calculation will not proceed. This
should ensure that the results obtained from a real space pseudopotential calculation accurately
reproduce those of a similar calculation using reciprocal space pseudopotentials.
Note: If this option in unchecked, the CASTEP calculation will be performed regardless of the quality
of the real space pseudopotential transformation.
Access methods

Electronic | More... | Potentials |
More...
More... | Potentials | More...
DFT-D tab
The DFT-D tab allows you to set up customized parameters for van der Waals dispersion corrections.
This can involve the definition of DFT-D corrections for exchange functionals that are not usually
supported, the definition of support for additional elements, or changing existing parameters.
Use custom DFT-D parameters: Specify whether to use custom DFT-D parameters. When this checkbox
is checked, select the van der Waals scheme to use from the dropdown list, options are:
TS (default)
Grimme
OBS
MBD*
Note: The option selected will automatically update the Use method for DFT-D correction setting on
the Setup tab of the CASTEP Calculation dialog.
Note: The schemes that rely on calculated electron densities, namely TS and MBD*, may not work
well in calculations with small unit cells, where the diameter of van der Waals spheres is comparable
to the lattice parameters. The MBD* scheme is particularly sensitive to such situations. In such cases,
the CASTEP output file contains a warning explaining the problem. The MBD* scheme can also fail if
the geometry is far from equilibrium, in which case it is useful to perform a preliminary geometry
optimization with the TS scheme. The main area of application of the MBD* scheme is molecular
crystals, so it may experience problems with highly ionic systems.
Atomic parameters
This table allows you to edit the dispersion correction parameters for each of the atomic species. The
type and number of parameters depend on the DFT-D scheme selected, please refer to the original
literature for the meaning and usage of each parameter.
The units for all parameters are in eV for energies and in Å for lengths. The available columns are:
Atom: Denotes the element to be edited.
C6 (eV Å6): Available for TS, MBD*, and Grimme schemes.
R0 (Å): Available for TS, MBD*, and Grimme schemes.

alpha (Å3): Available for TS, MBD*, and OBS schemes.

I (eV): Available for the OBS scheme.
Rvdw (Å): Available for the OBS scheme.
Note: Only the elements in the currently active document are listed in the Atomic parameters table .
Note: Each scheme includes a radius (R0 for TS and Grimme, Rvdw for OBS) that must be non-zero for
each of the active elements.
Scheme parameters
Scheme parameters are dimensionless numbers that define the functional form of each scheme.
Please refer to the original literature to for the meaning and usage of each parameter.
Depending on the van der Waals scheme selected for the custom DFT-D parameters setting, the Scheme
parameters that can be specified are:
TS: sR, d
Grimme: s6, d
OBS: lambda, n
MBD*: sR
Note: The default values for these parameters depend on the exchange correlation functional
selected on the Setup tab of the CASTEP Calculation dialog.
Note: Both scheme parameters must be non-zero for the calculations to start and for input files to be
written.
Reset All: Restores the default settings for each element in the grid.
Access methods

Electronic | More... | DFT-D
More... | DFT-D
Properties tab
The Properties tab allows you to select the properties that will be computed as part of a CASTEP
calculation.
Choose the properties you wish to compute by checking the appropriate checkboxes in the list. Once
you select a properties checkbox, additional options may be displayed below the list.
Access methods

Properties
Toolbar | Calculation | Properties

Band structure selection

Checking the Band structure checkbox on the Properties tab displays options for calculating electronic
energies along high symmetry directions in the Brillouin zone.
Energy range: Specify the maximum energy above the Fermi level for which band structure will be
calculated. Default = 10 eV.
k-point set: Specify the quality of the k-point set for the band structure calculation. Each setting
corresponds to a particular approximate separation between consecutive k-points on the reciprocal
space path. Default = Medium.

Coarse 0.04
Medium 0.025
Fine 0.015
Separation: Specify the approximate separation between k-points in Å-1. The default depends on the
selected k-point set.
More...: Provides access to the CASTEP Band Structure Options dialog, which allows you to set
additional parameters, including the reciprocal space path.
Access methods

Properties | Band structure
Toolbar | Calculation | Properties | Band
structure
CASTEP Band Structure Options dialog

The Band Structure Options dialog allows you to specify a custom reciprocal space path and the
eigenvalue convergence criterion used for band structure calculations.
Use separate XC functional for band structure calculation: When checked, allows you to select a
different exchange-correlation functional for the band structure calculation from the one used in the
self-consistent calculation.
Tip: This feature is particularly useful for carrying out expensive, screened exchange calculations.
Perform the main run with the LDA or GGA functional, then invoke screened or exact exchange in non
self-consistent mode during the band structure calculation.

Functional: Select the type of exchange-correlation potential to be used in the band structure
calculation.
Choose the type of functional from the first dropdown list. Available options are:
LDA
GGA
HF
HF-LDA
sX
sX-LDA
PBE0
B3LYP
HSE03
HSE06
Then, if appropriate, select the specific functional from the second dropdown list. Depending on the
functional type selected from the first dropdown list, some of the following options may be available:
CA-PZ
PBE
RPBE
PW91
WC
PBESOL
BLYP
Note: This option is enabled only when Use separate XC functional for band structure calculation is
checked.
Band energy tolerance: Specify the convergence criterion for electronic eigenvalues during the band
structure calculation. The calculation will stop when all electronic eigenvalues change by less than this
value over a single iteration of the electronic structure.
Note: More information about the symmetry labels used in the Band Structure Options dialog can be
found in Bradley and Cracknell (1972).
Path...: Provides access to the Brillouin Zone Path dialog, which allows you to specify a custom
reciprocal space path.
Access methods

Properties | More...
Toolbar | Calculation | Properties |
More...

Core level spectroscopy selection

Checking the Core level spectroscopy checkbox on the Properties tab displays options for calculating
core level spectra.
Energy range: Specify the energy limit above the Fermi level for which core level spectra will be
k-point set: Specify the quality of the k-point set for the core level spectroscopy calculation. Each setting
corresponds to a particular separation between consecutive k-points on the reciprocal space path.
Default = Medium.

Coarse 0.04
Medium 0.025
Fine 0.015
More...: Provides access to the CASTEP Core Level Spectroscopy Options dialog, which allows you to set
additional parameters, including the k-point set specification.
Access methods

Properties | Core level spectroscopy
Toolbar | Calculation | Properties | Core
level spectroscopy
CASTEP Core Level Spectroscopy Options dialog

The CASTEP Core Level Spectroscopy Options dialog allows you to specify the density of the k-point set
and the eigenvalue convergence criterion used for core level spectra calculations.
The Monkhorst-Pack k-point grid to be used in the calculation can be specified in one of four ways:
Coarse
Medium
Fine
The k-point separations associated with the three Quality settings are as follows:

Coarse 0.07
Medium 0.05
Fine 0.04

option is selected.
the system changes.
Band energy tolerance: Specify the convergence criterion in eV for electronic eigenvalues during the
core level spectroscopy calculation. The calculation will stop when all electronic eigenvalues change by
less than this value over a single iteration of the electronic structure.
Access methods

Properties | Core level spectroscopy |
More...
Toolbar | Calculation | Properties | Core
level spectroscopy | More...
Density of states selection

Checking the Density of states checkbox on the Properties tab displays options for calculating electronic
energies on the Monkhorst-Pack mesh of k-points.
Energy range: Specify the maximum energy above the Fermi level for which density of states will be
k-point set: Specify the quality of the k-point set for the density of states calculation. Each setting
corresponds to a particular separation between neighboring k-points in the Monkhorst-Pack grid.
Default = Medium.
Calculate PDOS: When checked, indicates that the information required to generate partial and local
densities of states will also be calculated.
More...: Provides access to the CASTEP Density of States Options dialog, which allows you to set

Access methods

Properties | Density of states
Density of states
CASTEP Density of States Options dialog

The CASTEP Density of States Options dialog allows you to specify the k-point set and the eigenvalue
convergence criterion used for density of states calculations.
Coarse
Medium
Fine

Coarse 0.07
Medium 0.05
Fine 0.04
option is selected.

the system changes.
Use separate XC functional for DOS calculation: When checked, indicates that a different exchange-
correlation functional will be used for the density of states calculation from the one used in the self-
consistent calculation.
Tip: This feature is particularly useful for carrying out expensive screened exchange calculations:
perform the main run with the LDA or GGA functional, then invoke screened or exact exchange in non-
self-consistent mode during the density of states calculation.
correlation potentials and the non-local exchange case. The potential used in the latter scenario
Functional: Select the type of DFT exchange-correlation potential to be used in the density of states
calculation.
LDA
GGA
HF
HF-LDA
sX
sX-LDA
PBE0
B3LYP
HSE03
HSE06
CA-PZ
PBE
RPBE
PW91
WC
PBESOL
BLYP
Note: The Functional control is enabled only if the Use separate XC functional for DOS calculation
checkbox is checked.

Band energy tolerance: Specify the convergence criterion, in eV, for electronic eigenvalues during the
density of states calculation. The calculation will stop when all electronic eigenvalues change by less than
this value over a single iteration of the electronic structure.
Access methods

Properties | Density of states | More...
Density of states | More...
Electron density difference selection

Checking the Electron density difference checkbox on the Properties tab displays options for calculating
an electron density difference field.
Calculation of atomic difference with respect to the sum of the densities of a subsystem requires that
sets of atoms have been created in the input structure. Only sets with DensityDifference as part of the
set name will be taken into account, and only if they contain atoms (it is possible for such sets to contain
other objects like bonds or monitors; only atoms will be considered in electron density difference
calculations). Use the Edit Sets dialog, accessed by selecting Edit | Edit Sets from the menu bar, to create
the required sets in the 3D Atomistic document.
Note: Sets of atoms should not overlap; that is, no atom can belong to more than one
'DensityDifference' set.
Tip: When only one set with the correct name is present in the structure, Materials Studio assumes
that the rest of the atoms should be treated as a second set. Thus, in the case of a molecule-surface
interaction, it is sufficient to create a single set that comprises all the atoms in the molecule.
Atomic densities: When selected, indicates that only the density difference with respect to the sum of
atomic densities will be calculated.
Sets of atoms: When selected, indicates that only the density difference with respect to the sum of the
densities of sets of atoms will be calculated.
Both atomic densities and sets of atoms: When selected, indicates that both kinds of density
difference will be calculated.
Access methods

Properties | Electron density difference
Electron localization function selection

Checking the Electron localization function checkbox on the Properties tab causes ELF to be calculated
as part of the CASTEP run.

Access methods

Properties | Electron localization
function
Electronic excitations (TD-DFT) selection

Checking the Electronic excitations (TD-DFT) checkbox on the Properties tab displays options for
calculating electronic excitations.
Calculate energies of: Specify the number of excited states which will be calculated. Default = 6.
The excitation data will be reported in the <seedname>_TDDFT.castep output file.
Calculate optical properties: If checked, the transition probabilities for these states will be calculated to
provide access to optical properties.
Optimize geometry for: Specify the excited state whose geometry should be optimized. Default = 1 (that
is, the first excited state).
The optimized structure for the specified state will be saved in the <seedname>_TDDFT_GO.xsd
output file.
Access methods

Properties | Electronic excitations (TD-
DFT)
Electronic excitations (TD-DFT)
NMR selection
Checking the NMR checkbox on the Properties tab displays options for calculating shielding tensors and
electric field gradients.
Shielding: Determines the chemical shielding tensor for each atom in the system.
Note: The shielding tensor is ill-defined for spin-polarized calculations. NMR calculations are allowed
wth a spin-polarized setting for a paramagnetic system, but you should check that the final electronic
state is indeed paramagnetic. Similarly, such calculations are not recommended for metallic systems
without a band gap; however, it is legitimate to use variable orbital occupancies and metallic settings
while modeling an insulator.
EFG: Determines the electric field gradients for each atom in the system.
J-coupling: Determines the J-coupling between the selected atom(s) and all other atoms in the system.
At least one atom must be selected in the input 3D Atomistic document.

Note: J-coupling can be calculated only for non-magnetic systems. The Relativistic treatment of the
OTFG pseudopotentials (on the Electronic tab of the CASTEP Calculation dialog) must be set to either
Schroedinger for non-relativistic treatment or ZORA for scalar-relativistic effects to be taken into
account. J-coupling calculations are supported only for systems with P1 symmetry. If your crystal has
symmetry other than P1, you will be prompted to convert the crystal symmetry to P1 before you can
continue.
G-tensor: Calculates the change in the EPR g-tensor for a molecule in a box or a defect in a crystal, as well
as the tensor of hyperfine parameters.
Note: The g-tensor and hyperfine parameters can only be calculated with spin-polarization turned on
and for systems with P1 symmetry. If your crystal has symmetry other than P1, you will be prompted
to convert the crystal symmetry to P1 before you continue.
System type: Specify the type of system used in the calculation. Options are:
Crystal
Molecule
Auto - CASTEP will assess the system and treat it as a crystal or molecule as appropriate
Note: Calculations in the Molecule mode can only be performed for systems with P1 symmetry. If
your crystal representing molecule in the box has symmetry other than P1, you will be prompted to
convert the crystal symmetry to P1 before you can continue.
More...: Provides access to the CASTEP NMR Options dialog, which allows you to specify the nuclear
quadrupolar moment for each element.
Note: Calculation of the NMR parameters requires higher accuracy for the wavefunctions than total
energy or geometry optimization calculations. This affects how you choose the Energy cutoff quality
parameter on the Electronic tab, even choosing Ultra-fine may not be sufficient to obtain high quality
NMR parameters. Therefore, it is advisable to study the convergence of the results as the Energy
cutoff parameter is increased. Generally, setting the cutoff to between 270 and 400 eV should
produce convergence of the shielding constant to about 1 ppm, but in some cases, the cutoff has to
be increased up to 550 eV.
Access methods

Properties | NMR
Toolbar | Calculation | Properties | NMR
CASTEP NMR Options dialog

The CASTEP NMR Options dialog allows you to set additional parameters affecting a NMR calculations.
Maximum number of steps: Specify the maximum number of conjugate gradient steps taken for each
electronic band in the electronic minimizer during an NMR calculation of the first-order perturbed
wavefunctions. Default = 250.
Nuclear quadrupolar moment
This section allows you to specify the nuclear quadrupolar moment, Q, used for electric field gradient
calculations. The value of the quadrupolar moment depends on the actual isotope. CASTEP makes a

suggestion based on the most typical isotope used in solid state NMR experiments. The value of Q
affects only the quadrupolar coupling constant, CQ, calculated and printed out by CASTEP. If you find
that the wrong value of Q was used you can rescale the generated CQ constant using a different Q value.
The list of default values is based on the compilation by Pyykkö (2008).
Note: CASTEP versions before Materials Studio 5.0 used an older compilation by Harris (1996), so
some results for quadrupolar coupling constants may have changed in later versions.
Q moment: Specify the nuclear quadrupolar moment of the element displayed. Change the element
type using the dropdown list.
Tip: To reset the nuclear quadrupolar moment for the displayed element to the default value, enter 0
for the Q moment.
Reset all Q values to defaults: Sets all nuclear quadrupolar moments for all elements to the default
values.

Properties | NMR | More...
Toolbar | Calculation | Properties | NMR
| More...
Optical properties selection

Checking the Optical properties checkbox on the Properties tab displays options for calculating
electronic intraband transitions.
Energy range: Specify the maximum energy above the Fermi level for which optical properties will be
Note: It is important to include a significant number of empty bands when calculating optical
properties. The exact number required will depend on the nature and size of the system under
consideration.
k-point set: Specify the quality of the k-point set for the optical properties calculation. Each setting
corresponds to a particular separation between neighboring k-points in the Monkhorst-Pack grid.
Default = Medium.
More...: Provides access to the CASTEP Optical Properties Options dialog, which allows you to set
Access methods

Properties | Optical properties
Optical properties

CASTEP Optical Properties Options dialog

The CASTEP Optical Properties Options dialog allows you to specify the density of the k-point set and the
eigenvalue convergence criterion used for optical properties calculations.
Coarse
Medium
Fine

Coarse 0.07
Medium 0.05
Fine 0.04
option is selected.
the system changes.
Use separate XC functional for optics calculation: When checked, indicates that a different exchange-
correlation functional will be used for the optical properties calculation from the one used in the self-
consistent calculation.

Tip: This feature is particularly useful for carrying out expensive, screened exchange calculations.
Perform the main run with the LDA or GGA functional, then invoke screened or exact exchange in non
self-consistent mode during the band structure calculation.
correlation potentials and the non-local exchange case. The potential used in the latter scenario
Functional: Select the type of DFT exchange-correlation potential to be used in the optical properties
calculation.
LDA
GGA
HF
HF-LDA
sX
sX-LDA
PBE0
B3LYP
HSE03
HSE06
CA-PZ
PBE
RPBE
PW91
WC
PBESOL
BLYP
Note: The Functional control is enabled only if the Use separate XC functional for optics calculation
Band energy tolerance: Specify the convergence criterion, in eV, for electronic eigenvalues during the
optical properties calculation. The calculation will stop when all electronic eigenvalues change by less
than this value over a single iteration of the electronic structure.

Access methods

Properties | Optical properties | More...
Optical properties | More...
Orbitals selection
Checking the Orbitals checkbox on the Properties tab causes the orbitals (wavefunctions) to be
calculated as part of the CASTEP run.
Note: Orbitals are required to calculate the STM profile.
Access methods

Properties | Orbitals
Orbitals
Phonons selection
Checking the Phonons checkbox on the Properties tab displays options for calculating phonon
properties.
Density of states: When checked, indicates that the phonon density of states will be computed as part
of the CASTEP run.
Dispersion: When checked, indicates that the phonon dispersion will be computed as part of the
CASTEP run.
Both: When selected both the phonon density of states and dispersion will be calculated during the
CASTEP run.
Calculate LO-TO splitting: When checked, indicates that a non-analytical correction to the dynamical
matrix will be applied. The LO-TO phonon frequency splitting at the Γ-point will be calculated along the
directions connecting the Γ-point with the neighboring points along the reciprocal space path. Default =
checked.
Method: Select the technique to be used to calculate phonon frequencies from the dropdown list.
Linear response
Finite displacement
Finite displacement phonons are available only at the commensurate q-points (at the cost of creating a
supercell). However, in this case, the phonon frequencies can be obtained with no limitations on the
settings or the physical properties of the system. The finite displacement technique can be used for
metals, ultrasoft potentials, spin-polarized systems, and so on.

Note: If LO-TO splitting is requested, then the restrictions on the system type and settings (insulator,
norm-conserving potentials, non-spin-polarized calculation) are the same for both the linear response
and finite displacement techniques.
More...: Provides access to the CASTEP Phonon Properties Setup dialog, which allows you to set
additional parameters affecting a phonon calculation, including the convergence tolerance.
Access methods

Properties | Phonons
Phonons
CASTEP Phonon Properties Setup dialog

The CASTEP Phonon Properties Setup dialog allows you to set additional parameters affecting a phonon
calculation.
Method: Select the technique to be used to calculate phonon frequencies from the dropdown list.
Linear response
Finite displacement
The finite displacement technique can be used for metals, ultrasoft potentials, spin-polarized systems,
and so on, and allows you to obtain phonon frequencies with no limitations on the settings or the
physical properties of the system.
Note: If LO-TO splitting is requested (that is, by checking the Calculate LO-TO splitting checkbox on
the Properties tab of the CASTEP Calculation dialog when Phonons is selected), then the restrictions
on the system type and settings (insulator, norm-conserving potentials, non-spin-polarized) are the
same for both the linear response and finite displacement techniques.
Linear response
Use interpolation: When checked, indicates that the real space dynamical matrix will be calculated using
the Monkhorst-Pack mesh defined by the separation parameter.
q-vector grid spacing for interpolation: Specify the q-point separation parameter, in Å-1, which
represents the average distance between Monkhorst-Pack mesh q-points used in the real space
dynamical matrix calculations. A smaller separation parameter produces a denser mesh, giving more
accurate results at the expense of longer calculation times.
Note: The q-vector grid spacing for interpolation control is enabled only if the Use interpolation
Convergence tolerance: Specify the convergence criterion, in eV Å-2, for the force constants during a
phonon properties run.
Note: The Convergence tolerance control is enabled only if Linear response is selected from the
Method dropdown list.
Finite displacement
Use: Select the method to calculate the dynamic matrix using finite displacement. Available options are:

Several small supercells - uses the Monkhorst-Pack mesh defined by the separation parameter.
When Method is set to Finite displacement this invokes the nondiagonal supercell approach of
Lloyd-Williams and Monserrat (2015).
One large supercell
q-vector grid spacing for interpolation: Specify the q-point separation parameter, in Å-1. This
represents the average distance between Monkhorst-Pack mesh q-points used in the real space
dynamic matrix calculations. A smaller separation parameter produces a denser mesh, giving more
accurate results at the expense of longer calculation times.
Note: The q-vector grid spacing for interpolation control is enabled only if Several small supercells is
selected.
Supercell defined by cutoff radius: Specify the real space cutoff radius, in Å, for dynamical matrix
calculations. This value will be used to construct an appropriate supercell. A larger cutoff radius
produces more accurate results at the expense of longer calculation times.
If the cutoff radius specified creates a large supercell, its size is reported as a factor of the size of the
current cell, indicating that the calculation may be computationally expensive. If the cutoff radius is
reasonable, it is confirmed that the original cell is large enough. For non-3D periodic systems a reminder
that a supercell cannot be constructed is displayed.
Note: The Supercell defined by cutoff radius control is enabled only if One large supercell is selected.
Dispersion
Quality: Set the quality of the q-vector set for the phonon dispersion calculation. The quality level
affects the approximate separation between consecutive q-vectors on the reciprocal space path.
Available options and the corresponding q-vector separations are:
Quality q-vector separation (Å-1)

Coarse 0.04
Medium 0.025
Fine 0.015
Separation: Specify the approximate separation between q-vectors in Å-1. The default depends on the
selected Quality of the q-vector.
Path...: Provides access to the Brillouin Zone Path dialog, which allows you to specify a custom
reciprocal space path.
Density of states
Quality: Set the quality of the q-vector set for the phonon density of states calculation. The quality level
affects the separation between neighboring q-vectors in the Monkhorst-Pack grid. Available options and
the corresponding q-vector separations are:

Gamma a single q-vector at (0,0,0) will be used
Coarse 0.07
Medium 0.05
Fine 0.04

Note: For Linear response calculations, if Gamma point is selected and the Use interpolation
checkbox is checked frequencies will be calculated using interpolation method. This involves
calculations of phonon frequencies at multiple q-vectors in the Brillouin zone and is therefore an
expensive way of generating Gamma point phonons. Such calculations can be justified only as a way
of testing the accuracy of interpolation scheme (directly calculated frequencies are more accurate). To
run calculations only at the Gamma point you should uncheck the Use interpolation checkbox.
More...: Provides access to the CASTEP Phonon Density of States Options dialog, which allows you to
specify the q-vector set.
Access methods

Properties | Phonons | More...
Phonons | More...
CASTEP Phonon Density of States Options dialog

The CASTEP Phonon Density of States Options dialog allows you to specify the q-vector set for phonon
density of states calculations.
The Monkhorst-Pack q-vector grid to be used in the calculation can be specified in one of four ways.
Note: The option selected here propagates from the Quality setting in the Density of States section
on the CASTEP Phonon Properties Setup dialog. As a result, altering the selection here will also change
the setting on the CASTEP Phonon Properties Options dialog.
Gamma point only: When selected, indicates that a single q-vector at (0,0,0) will be used for the density
Quality: When selected, indicates that the q-vector grid will be generated using a q-vector separation
Available options and the associated q-vector separations are:

Coarse 0.07
Medium 0.05
Fine 0.04
Separation: When selected, indicates that the q-vector grid will be generated according to the specified
q-vector separation. Specify the q-vector separation, in Å-1, in the associated text box.
Note: When the Separation option is selected, the Monkhorst-Pack parameters are derived so as to
produce the specified separation between neighboring grid points.
Custom grid parameters: When selected, indicates that the q-vector grid will be generated using the

option is selected.
Display points...: Displays, in a new window, the number and fractional coordinates of the reciprocal
space mesh points that would be generated using the currently specified parameters.
Note: The actual set of q-vectors that will be used in the calculation may be altered if the symmetry of
the system changes.
Access methods

Properties | Phonons | More... |
More...
Phonons | More... | More...
Polarizability, IR and Raman spectra selection

Checking the Polarizability, IR and Raman spectra checkbox on the Properties tab displays options for
calculating dielectric permittivity and molecular polarizability.
System type: Select the option from the dropdown list that best describes the system being studied or
choose Auto for automatic detection. Available options are:
Auto
Crystal
Molecule
Linear
Calculate Raman intensities: When checked, activities for Raman active vibrations will be calculated.
Subsequently CASTEP analysis can be used to construct Raman mode intensities for a given
temperature and laser wavelength from calculated activities.
More...: Provides access to the CASTEP IR and Raman Options dialog, which allows you to set additional
parameters affecting a polarizability, IR and Raman calculation, including the convergence tolerance and
Raman frequency range.
Access methods

Properties | Polarizability, IR and
Raman spectra
Polarizability, IR and Raman spectra

CASTEP IR and Raman Options dialog

The CASTEP IR and Raman Options dialog allows you to set additional parameters affecting a
polarizability, IR, and Raman calculation.
Convergence tolerance: Specify the value, in Å3, of the required convergence for the second-order
response to the electric field. Default = 1.0e-5 Å3.
Scissors operator: Specify the value, in eV, of the scissors operator to be used in calculating the
response to the electric field.
Method: Select the technique to use to calculate Raman intensities from the dropdown list. Available
options are:
Linear response
Finite displacement
Initial frequency: Specify the value, in cm-1, of the minimal frequency for which Raman modes are
calculated. Default = 0 cm-1.
Final frequency: Specify the value, in cm-1, of the maximal frequency for which Raman modes are
calculated. Default = 10000 cm-1.
Note: The frequency range can only be specified only if Method is set to Finite displacement.
Access methods

Properties | Polarizability, IR and
Raman spectra | More...
Polarizability, IR and Raman spectra |
More...
Population analysis selection

The Population analysis checkbox is checked by default. When this is checked the Properties tab
displays options for controlling the calculation of Mulliken charges (including partial charges for each
angular momentum component), Mulliken spins (for spin-polarized calculations), and Mulliken bond
populations. Hirshfeld charges are always calculated when the Population analysis checkbox is checked.
Distance cutoff for bond populations: Specify the maximum interatomic distance, in Å, to be
considered in the bond population calculation. Default = 3.0 Å.
Calculate band populations: When checked, indicates that the contribution to Mulliken populations
from each band will be calculated, in addition to the Mulliken charges.
Note: For disordered crystals population analysis cannot be performed and any these settings will be
not be used.

Access methods

Properties | Population analysis
Population analysis
Stress selection
Checking the Stress checkbox on the Properties tab causes the stress tensor to be calculated as part of
the CASTEP run.
Access methods

Properties | Stress
Toolbar | Calculation | Properties | Stress
Job Control tab

CASTEP calculations run in the background on a server using the gateway. The Job Control tab allows
you to select a server for the CASTEP calculation and to control some aspects of how the calculation will
be performed.
Note: The options specified on the Job Control tab only apply to new jobs. They do not affect jobs
that are already running.
Gateway location: Select a server for the CASTEP calculation from the list of available server machines.
You can add servers to the list using the Server Console.
Queue: Specify the queue to which the job will be submitted. Select the desired queue from the
dropdown list, which displays the available queues on the chosen gateway. See Working with queues for
additional details.
Job description: Specify the name to be used to identify the job.
A default job description is automatically assigned. An alternative description can be chosen by
unchecking the Automatic checkbox and entering the new name in the Job description text box.
Note: Do not use this field for Properties task since in this case CASTEP Analysis will not be able to
associate results files with the original structure.
Automatic: When checked, indicates that a job description will be selected automatically. Default =
checked.
Run in parallel on: Indicates that the job will be run on the selected gateway using the specified number
of computer cores. The text to the right of the Run in parallel on control indicates the maximum number
of cores available on the selected gateway.
Note: It is recommended to use the number of cores which is commensurate with the number of k-
points in the calculation. You can determine the number of k-points by using the Display points...
button on the k-points tab of the CASTEP Electronic Options dialog.

Using up to: Specify the maximum number of threads allowed to be used by each MPI process. If the
number of threads is greater than 1, the hybrid OpenMP/MPI parallelization will be invoked. The actual
number of threads in use will depend on the details of the hardware configuration and the queuing
system setup. For example, under with some queuing systems you can set up the gateway to guarantee
exclusive use of nodes when number of threads is greater than 1.
Note: This functionality is available only on Linux gateways. To ensure it works as expected when a
gateway is using a queuing system, check that the queuing system is set up consistently. See Working
with queues for additional details.
Note: Hybrid OpenMP/MPI parallelization can substantially decrease the amount of memory
required for a job (though it could somewhat decrease speed).
Runtime optimization: Specify the strategy used to balance memory use and speed during the
calculation. Available options are:
Default - Balance speed and memory use. Wavefunction coefficients for all k-points in a calculation
will be kept in memory during, rather than be paged to disk. Some large work arrays will be paged to
disk.
Memory - Minimize memory use. All wavefunctions and large work arrays are paged to disk.
Speed - Maximize speed. No paging to disk.
Note: This option does not apply to calculations using the nonlocal exchange correlation potential. In
this case paging does not save any memory and Speed optimization is enforced.
More...: Provides access to the CASTEP Job Control Options dialog which allows you to set additional
options associated with monitoring and controlling the results of a CASTEP calculation.
Access methods
Menu Modules | CASTEP | Calculation | Job

Control
Toolbar | Calculation | Job Control
CASTEP Job Control Options dialog

The CASTEP Job Control Options dialog allows you to set the options associated with monitoring and
controlling the results of a CASTEP calculation.
Update structure: When checked, indicates that intermediate results will be used to update the
displayed structure as the job progresses. Default = unchecked.
Update graphs: When checked, indicates that intermediate results will be used to update the displayed
graphs as the job progresses. Default = checked.
Update textual results: When checked, indicates that intermediate results will be used to update
textual results files as the job progresses. Default = checked.
Tip: Intermediate updates are useful shortly after initiating a job to assess if it is progressing as
expected.
Update every: Specify the time interval, in seconds, between requests for intermediate updates.

Note: The rate at which new results appear is limited by the time it takes for the CASTEP server to
perform a single iteration step of the chosen task. This may be significantly longer than the chosen
update interval.
Retain server files: When checked, indicates that the folder on the server containing the job files will be
retained after the job is complete. Default = unchecked.
If this checkbox is left unchecked, the job files on the server will be deleted. Regardless of whether it is
checked or unchecked, copies of the results files will always be retrieved from the server, placed in the
associated project on the local machine, and displayed in the Project Explorer.
Tip: It may be useful to retain the server files so that standalone CASTEP runs can performed.
Automatically view output: When checked, the output files from the job will be opened automatically
when the calculation is completed. Files opened may include a structure document and a CASTEP
output (.castep) file for the main task performed by the job. Default = checked.
Notify on job completion: When checked, indicates that a dialog will be displayed when the job is
complete. Default = checked.
Tip: If you run several short jobs in one session, you may find it useful to stop the automatic display
of job completion notices and results files.
Return BibTeX list of references: When checked, indicates that a BibTeX formatted list of references
used for this run will be returned when the job has completed.
Return complete check file: When checked, indicates that the full check file will be returned when the
job has completes. Availability of this file (which can be very large) can accelerate the restart of a job.
Note: This option does not apply to calculations using the nonlocal exchange correlation potential. In
this case the check file is always returned so that restarts are enabled.
Access methods
Menu Modules | CASTEP | Calculation | Job

Control | More...
Toolbar | Calculation | Job Control |
More...
CASTEP Job Files dialog

The CASTEP Job Files dialog allows you to save input files for a CASTEP calculation without running the
job, or to run a job using an existing set of input files.
This functionality is provided for users who need to run the CASTEP server program in standalone mode,
or who wish to edit the CASTEP input files in order to gain access to features not supported by the
CASTEP interface.
Save Files: Saves the input files required to run the CASTEP job on the server but does not submit the
job.
Note: The Save Files button is enabled only when the current 3D model document contains a suitable
periodic structure.

The input files are placed in a subfolder of the current Materials Studio project directory and the primary
CASTEP input (.param) file is displayed in the Project Explorer.
Run Files: Runs a CASTEP job using an existing set of input files.
Note: The Run Files button is enabled only when the current document is a CASTEP input (.param)
file.
The job is submitted using the settings specified on the Job Control tab.
The results files will be placed in a subfolder of the current Materials Studio project directory.
When band structure, density of states or optical properties are requested, additional input files will be
produced for each property. This is because these properties must each be calculated using a separate
run of the CASTEP server. These additional input files are named according to the property they are
intended to calculate.
In such situations, selecting the input file for the main task and pressing the Run Files button runs all of
the input files in a single job.
Access methods

Files...
Toolbar | Calculation | Files...
CASTEP Analysis dialog

The Analysis dialog allows you to analyze the results of a CASTEP calculation.
A list of properties that may be analyzed is displayed at the top of the dialog.
Select the property you wish to analyze from the list. Options relating to analysis of that property are
displayed at the bottom of the dialog.
Help: Displays the Help topic for the currently selected analysis.
Access methods
Menu Modules | CASTEP | Analysis

Toolbar | Analysis
Band structure selection

The following options are available when Band structure is selected from the list of properties.
Results file: Select the CASTEP results file from which the band structure information will be taken.
When more than one set of results is available, use the button to browse the current directory and
appropriate subdirectories for results files.
Energy units: Specify the energy units to be used for the dispersion graph. Available options are:
eV
Ha

Scissors: Specify the scissors operator to be used in plotting the band structure.
The scissors operator is only applied for insulating systems, which have a clear separation between
valence band and conduction band states. It is ignored for metallic systems.
Graph style: Specify the style to be used for the band structure graph. Available options are:
Points
Line
Show DOS: When checked, indicates that a density of states from the specified results file will be
displayed, together with the band structure graph.
Full DOS: When selected, indicates that the total density of states will be displayed.
Partial: When selected, indicates that the partial density of states (PDOS) will be displayed.
The angular momenta to be included in the PDOS display can be controlled using the s, p, d, f, and Sum
checkboxes.
Note: When the appropriate structure document is active and atoms are selected, the contribution
to the density of states from the selected atoms will be plotted. Otherwise, the contribution from all
atoms is considered.
Display DOS: Specify which spin components should be plotted in the density of states graph. For a
spin-polarized calculation, the supported options are:
Total - contributions from both spin-up and spin-down eigenstates are summed
Alpha - contributions from spin-up eigenstates only
Beta - contributions from spin-down eigenstates only
Alpha and Beta - contributions from both spin-up and spin-down eigenstates are displayed in a
butterfly plot
Spin - difference between contributions from spin-up and spin-down eigenstates is displayed
Total and Spin
When a non-spin-polarized CASTEP calculation is analyzed, only the Total option is available.
Function: Specify whether to plot the untreated DOS or the integrated density of states (the number of
states).
More...: Provides access to the CASTEP DOS Analysis Options dialog which allows you to specify
parameters controlling the density of states integration method.
Note: The Full, Partial, Display DOS, and More... options are enabled only if Show DOS is checked.
View: Displays the band structure using the options specified.
spin is not optimized two charts will automatically be displayed, <seedname> Band
Structure Alpha.xcd and <seedname> Band Structure Beta.xcd.
Access methods
Menu Modules | CASTEP | Analysis | Band

structure
Toolbar | Analysis | Band structure

Core level spectroscopy selection

The following options are available when Core level spectroscopy is selected from the list of properties.
Results file: Select the CASTEP results file from which the core level spectroscopy information will be
taken. When more than one set of results is available, use the button to browse the current
directory and appropriate subdirectories for results files.
Note: Core level spectra can only be calculated for single atoms. One atom should be selected in the
active 3D Atomistic document before carrying out a core level spectroscopy analysis.
Tip: If you included a core hole in your calculation, you can select the relevant atom using the Atom
Selection dialog.
Spectrum: Specify the type of spectrum that will be calculated. If there is a core hole in the shell a *
symbol is included in the spectrum name, for example 1s*[K1]. Available options (with and without core
holes) are:
1s[K1]
2s[L1]
2p[L23]
3s[M1]
3p[M23]
3d[M45]
4s[N1]
4p[N23]
4d[N45]
5s[O1]
5p[O23]
Type: Specify the type of spectrum that will be calculated. Available options are:
Absorption - the predicted absorption spectrum
Emission - the predicted emission spectrum
More...: Opens the CASTEP EELS Analysis Options dialog.
Calculation: Specify the polarization of the incident radiation for the core level spectroscopy calculation.
Polarization: Specify the direction of the polarization of the incident radiation in fractional (lattice)
coordinates. Not available when Unpolarized is selected for Calculation.
Atom Selection...: Opens the Atom Selection dialog.
View: Displays the selected core level spectrum.
A chart document is created using the information contained in the active grid document.
Note: If the requested spectrum is not available, a warning message will be returned explaining the
reasons.

Access methods
Menu Modules | CASTEP | Analysis | Core

level spectroscopy
Toolbar | Analysis | Core level
spectroscopy
CASTEP EELS Analysis Options dialog

The CASTEP EELS Analysis Options dialog allows you to specify the parameters controlling the core level
spectroscopy broadening options.
Spectrum: Reports the spectrum specified on the CASTEP Analysis dialog when Core level spectroscopy
is selected.
Instrumental smearing: Specify the Gaussian broadening from the instrument to be used.
Default = 0.2 eV.
Lifetime effects: When checked, lifetime broadening effects will be taken into account.
Core level broadening: Specify the broadening to be used at the core level. Default values for lifetime
broadening are tabulated based on the compilation by Fuggle and Inglesfield (1992).
Reset broadening to default: Resets the Core level broadening to its default value.
Include spin-orbit splitting: When checked, spin-orbit splitting for the core level is added to the
spectrum.
Spin-orbit splitting: Specify the value of the core level spin-orbit splitting to be used. Default values for
spin-orbit splitting are taken from atomic spectroscopic data (see the WebElements Periodic Table:
http://www.webelements.com). These values represent the difference between reported binding
energies for core electrons of the given species, for example the difference between 2p 1/2 and 2p 3/2
gives the L2,3 splitting.
Reset spin-orbit splitting to default: Resets the Spin-orbit splitting to its default value.
Normalize spectrum: When checked, the resulting spectrum will be normalized to 1 at maximum.
Access methods
Menu Modules | CASTEP | Analysis | Core

level spectroscopy | More...
Toolbar | Analysis | Core level
spectroscopy | More...
Density of states selection

The following options are available when Density of states is selected from the list of properties.
Results file: Select the CASTEP results file from which the density of states information will be taken.
Energy units: Specify the energy units to be used for the density of states graph. Available options are:

eV
Ha
Full DOS: When selected, indicates that the total density of states will be displayed.
Partial: When selected, indicates that the partial density of states (PDOS) will be displayed.
Note: PDOS analysis formalism is not valid for high energy states in the conduction band: PDOS
representation will usually decay to zero at about 20 eV above the Fermi level. This is related to the
fact that expansion of essentially free electron states in terms of a limited number of atomic-like basis
functions is impossible to carry out with any degree of accuracy. Only the valence band and lower
part of the conduction band are meaningful in the PDOS plot.
The angular momenta to be included in the PDOS display can be controlled using the s, p, d, f, and Sum
checkboxes.
Note: When the appropriate structure document is active and atoms are selected, the contribution
to the density of states from the selected atoms will be plotted. Otherwise, the contribution from all
Display DOS: Specify which spin components should be plotted in the density of states graph. For a
spin-polarized calculation, the supported options are:
Total - contributions from both spin-up and spin-down eigenstates are summed
Alpha - contributions from spin-up eigenstates only
Beta - contributions from spin-down eigenstates only
Alpha and Beta - contributions from both spin-up and spin-down eigenstates are displayed in a
butterfly plot
Spin - difference between contributions from spin-up and spin-down eigenstates is displayed
Total and Spin
When a non-spin-polarized CASTEP calculation is analyzed, only the Total option is available.
spin is not optimized only the Total option is available. In this case, two charts will automatically be
displayed, <seedname> DOS Alpha.xcd and <seedname> DOS Beta.xcd.
Function: Specify whether to plot the untreated DOS or the integrated density of states (the number of
states).
Scissors: Specify the scissors operator to be used in plotting the density of states.
Atom Selection...: Opens the Atom Selection dialog.
More...: Provides access to the CASTEP DOS Analysis Options dialog, which allows you to specify
parameters controlling the density of states integration method.
View: Displays the density of states using the options specified.
Access methods
Menu Modules | CASTEP | Analysis | Density

of states

Toolbar | Analysis | Density of states
CASTEP DOS Analysis Options dialog

The CASTEP DOS Analysis Options dialog allows you to specify the parameters controlling the density of
states integration method.
Integration method: Select the method to be used for integrating the density of states results from the
dropdown list. Supported methods are:
Smearing - Gaussian broadening is applied to the eigenvalues obtained from the CASTEP calculation.
Interpolation - eigenvalues (and partial weights for a partial density of states) from the CASTEP
calculation are interpolated onto a finer k-point grid.
The Interpolation method provides an improved representation of the density of states. However, it can
only be used when eigenvalues are available on a Monkhorst-Pack grid with 3 or more points in each
direction. The k-point set for density of states calculations can be specified on the CASTEP Density of
States Options - Properties tab on the CASTEP Calculation dialog. If the Interpolation method cannot be
used for the selected results, it will be absent from the dropdown list.
Smearing width: Specify the Gaussian broadening to be used.
Note: This option is enabled only if the Smearing integration method is selected.
Accuracy level: Specify the quality of the interpolation to be used. Available options are:
Coarse - Interpolates onto a k-point grid of about 50×50×50
Medium - Interpolates onto a k-point grid of about 100×100×100
Fine - Interpolates onto a k-point grid of about 200×200×200
Instrument broadening: Specify an additional broadening to be applied to the interpolated density of
states.
Note: The Accuracy level and Instrument broadening options are enabled only if the Interpolation
integration method is selected.
Number of points per: Specify number of points per 1 eV or per 1 Ha energy range. Use high settings to
generate charts that remain smooth after a zoom-in operation.
OK: Updates the settings with any changes and closes the dialog.
Cancel: Closes the dialog without updating any settings.
Access methods
Menu Modules | CASTEP | Analysis | Density

of states | More...
Menu Modules | CASTEP | Analysis | Band
structure | More...
Toolbar | Analysis | Density of states |
More...

Toolbar | Analysis | Band structure |

More...
Elastic constants selection

The following options are available when Elastic constants is selected from the list of properties.
Results file: Select the CASTEP results file from which the elastic constants information will be taken.
Calculate: Analyzes stress-strain relationship and calculates the tensors of the elastic constants and the
compliances. These results are used to produce the bulk modulus, compressibility, averaged sound
velocity, elastic Debye temperature, Young modulus, Poisson ratio, Lamé constants, Vickers hardness,
and universal anisotropy index. All of these properties including polycrystalline averages using Voigt,
Reuss, and Hill schemes, are written to a new text document, seedname Elastic
Constants.txt, in the results folder.
Note: The empirical expression for Vickers hardness cannot be applied if the calculated shear
modulus is negative (this can happen, for example, when the calculation settings are not sufficiently
accurate). In such a case the summary report will not include the hardness.
Access methods
Menu Modules | CASTEP | Analysis | Elastic

constants
Toolbar | Analysis | Elastic constants
Electron density selection

The following options are available when Electron density is selected from the list of properties.
Results file: Select the CASTEP results file from which the electron density information will be taken.
Density field: Select the type of density field to be imported. For a spin-polarized calculation, the
supported options are:
Total density - the total electron density
Spin density - the difference between alpha- and beta-electron densities
Alpha density - the density of spin-up electrons
Beta density - the density of spin-down electrons
When a non-spin-polarized CASTEP calculation is analyzed, only the Total density option is available.
View isosurface on import: When checked, an isosurface will be created automatically when the
density field is imported.
Save density to file: Creates a plain text file that contains either the charge density or, for spin-polarized
calculations, the charge and spin density on a uniform grid in real space. The file has the extension
.charg_frm.

Note: This file is hidden by default. Use the Tools | Folder Options... | View | Show hidden files and
folders option in the Windows File Explorer to access the file.
Import: Imports the selected density field from the CASTEP results file into the current structure
document.
Access methods
Menu Modules | CASTEP | Analysis | Electron

density
Toolbar | Analysis | Electron density
Electron density difference selection

The following options are available when Electron density difference is selected from the list of
properties.
Results file: Select the CASTEP results file from which the information required to visualize the electron
density difference will be taken. When more than one set of results is available, use the button to
browse the current directory and appropriate subdirectories for results files.
Use atomic densities: When checked, the electron density difference with respect to the sum of the
atomic densities will be created. If unchecked, the density difference with respect to the sum of the
densities of sets of atoms will be created.
electron density difference field is imported.
Import: Imports the selected electron density difference field from the CASTEP results file into the
current structure document.
Note: Analysis based on atomic densities requires the presence of a binary file with the extension
.chdiff; analysis based on sets of atoms requires that for each set of input files, seed_
Subset*.*, there are binary files with the extension .check present.
Access methods

density difference
Toolbar | Analysis | Electron density
difference
Electron localization function selection

The following options are available when Electron localization function is selected from the list of
properties.
Results file: Select the CASTEP results file from which the ELF information will be taken. When more than
one set of results is available, use the button to browse the current directory and appropriate
subdirectories for results files.

View isosurface on import: When checked, an isosurface will be created automatically when the ELF
field is imported.
Import: Imports the ELF field from the CASTEP results file into the current structure document.
Access methods

localization function
Toolbar | Analysis | Electron localization
function
Energy evolution selection

The following options are available when Energy evolution is selected from the list of properties.
Results file: Select the CASTEP results file from which the energy evolution information will be taken.
View: Generates chart documents as described in the Displaying trajectory and chart data topic.
These charts are the same as would be generated by selecting Update graphs in the CASTEP Job Control
Options dialog. Charts generated using Energy evolution can be generated whether or not you chose
Update graphs in the original calculation.
Note: Each time you select Update graphs the existing chart documents are rewritten, and any
changes or annotations you have made to the charts will be lost.
Access methods
Menu Modules | CASTEP | Analysis | Energy

evolution
Toolbar | Analysis | Energy evolution
Fermi surface selection

The following options are available when Fermi surface is selected from the list of properties.
Results file: Select the CASTEP results file from which the band structure data will be taken. When more
than one set of results is available, use the button to browse the current directory and appropriate
Filter: Choose how to filter the available Fermi surfaces, options are:
All - all Fermi surfaces are available.
Show only bands crossing Fermi level: When checked only the bands which traverse the Fermi level
will be listed in the table below.

Band - the index of the band in this row

Spin - the spin for this band
From - lowest value of the energy for the band (in eV)
To - highest value of the energy for the band (in eV)
Import: Imports the selected Fermi surface from the CASTEP results file into the current structure
document.
Access methods
Menu Modules | CASTEP | Analysis | Fermi

surface
Toolbar | Analysis | Fermi surface
IR spectrum selection
The following options are available when IR spectrum is selected from the list of properties.
Results file: Select the CASTEP results file from which the Hessian (dynamical matrix) and ATP tensor
(Born charges) information will be taken. When more than one set of results are available, use the
button to browse the current directory and appropriate subdirectories for results files.
Import Hessian from CASTEP output: Imports the Hessian and ATP tensor data, if present, from the
selected CASTEP results file into the current structure document.
Note: This only is enabled if the currently active document contains a structure for which CASTEP
results for the dynamical matrix at the Γ-point are available.
Once a Hessian has been imported, vibrational mode frequencies and, if ATP tensors were calculated,
absorption intensities can be displayed in the form of a list of values or graphically as a vibrational
spectrum using the Vibrational Analysis tool.
View vibrational analysis: Opens the Vibrational Analysis dialog. This is only enabled when the Hessian
is imported into the current structure document.
Access methods
Menu Modules | CASTEP | Analysis | IR

spectrum
Toolbar | Analysis | IR spectrum
NMR selection
The following options are available when NMR is selected from the list of properties.
Results file: Select the CASTEP results file from which the NMR information will be taken. When more

Assign isotropic chemical shielding to structure: Adds the NMRShielding property to the atoms for
which NMR shielding data are available.
Assign electric field gradients to structure: Adds the EFGQuadrupolarCoupling and EFGAsymmetry
properties to the atoms for which electric field gradient data are available.
Once added, all three of these properties are accessible in the Properties Explorer and can be used for
labeling.
Show J-coupling constants: Generates and opens a study table reporting the calculated J-coupling
constants. This option is only available when the Results file selector is set to use a seedname_
NMRJC.castep file.
Access methods
Menu Modules | CASTEP | Analysis | NMR

Toolbar | Analysis | NMR
Optical properties selection

The following options are available when Optical properties is selected from the list of properties.
Results file: Select the CASTEP results file from which the optical properties information will be taken.
Calculation: Specify the type of optical properties calculation to be performed. Available options are:
Polarized - optical properties are calculated for plane polarized light with the specified polarization
direction.
Unpolarized - optical properties are averaged over polarization directions perpendicular to the
specified incident direction.
Polycrystalline - optical properties are averaged over all polarization directions, thereby imitating an
experiment on a polycrystalline sample.
Smearing: Specify the Gaussian broadening to be used for calculating the dielectric function.
Scissors: Specify the scissors operator to be used for calculating the dielectric function.
Polarization: Specify the polarization of the incident radiation for the optical properties calculation. The
direction is specified in fractional (lattice) coordinates.
Note: This option is enabled only if a Polarized calculation is selected.
Incidence: Specify the incident direction of radiation the for optical properties calculation. The direction
is specified in fractional (lattice) coordinates.
Note: This option is enabled only if an Unpolarized calculation is selected.
Function: Specify which optical property should be displayed as a function of frequency when the View
button is pressed. Available options are:

Reflectivity
Absorption
Refractive Index - both the real part, n, and imaginary part, k, of the complex optical constant are
displayed.
Dielectric Function - both the real and imaginary parts are displayed.
Conductivity - both the real and imaginary parts are displayed.
Loss Function
Units: Specify the frequency units used for the display of optical properties.
More...: Provides access to the Optics Analysis Options dialog, which allows you to specify any Drude
contribution to the optical properties.
Calculate: Calculates the dielectric function from the optical matrix elements and eigenvalues in the
CASTEP results file.
A grid document is produced containing the calculated dielectric function.
View: Displays the selected optical property as a function of frequency.
Note: This button is enabled only if the current document is a grid document containing a dielectric
function.
A chart document is created using the dielectric function information contained in the active grid
document.
Access methods
Menu Modules | CASTEP | Analysis | Optical

properties
Toolbar | Analysis | Optical properties
Optics Analysis Options dialog

The CASTEP Optics Analysis Options dialog allows you to specify the Drude contribution to the optical
properties.
Plasma frequency: Specify the value of the plasma frequency which is used in the Drude term.
Tip: A value of zero, no Drude correction, should be used for insulators and semiconductors. For
metals, a typical value range is 2-10 eV.
Drude damping: Specify the lifetime broadening for the Drude contribution.
Tip: Typical values range from 0.02 eV to 0.08 eV.

Access methods
Menu Modules | CASTEP | Analysis | Optical

properties | More...
Toolbar | Analysis | Optical properties |
More...
Orbitals selection
The following options are available when Orbitals is selected from the list of properties.
Results file: Select the CASTEP results file from which the orbitals information will be taken. When more
Filter: Choose which orbitals are displayed in the table:
Alpha - displays data only for alpha-spin orbitals (spin up)
Beta - displays data only for beta-spin orbitals (spin down)
Note: For non-spin-polarized calculations, this option is not available.
The orbital analysis table, below the Filter dropdown list, lists the eigenvalues and other information
about each orbital. The list starts with the lowest energy orbital. Other information contained in the
table includes:
N - number of the orbital, with 1 corresponding to the lowest energy orbital
s - spin, + for alpha, and - for beta.
Note: In a non-spin-polarized calculation, all orbitals are labeled +.
From - lowest value of the energy of the Nth band at any k-point (in eV)
To - highest value of the energy of the Nth band at any k-point (in eV)
Scissors: Specify the scissors operator to be used in displaying the orbital eigenvalues.
View isosurface on import: When checked, an isosurface will be created automatically when the orbital
field is imported. The units for the isovalues are e/Å3.
Import: Imports the selected orbital field from the CASTEP results file into the current structure
document.
Access methods
Menu Modules | CASTEP | Analysis | Orbitals

Toolbar | Analysis | Orbitals
Phonon dispersion selection

The following options are available when Phonon dispersion is selected from the list of properties.

Results file: Select the CASTEP results file from which the phonon dispersion information will be taken.
Units: Specify the frequency units to be used for the phonon dispersion graph. Available options are:
THz
meV
cm-1
Graph style: Specify the style to be used for the band structure graph. Available options are:
Points
Line
Show DOS: When checked, indicates that a phonon density of states from the specified results file will
be displayed, together with the phonon dispersion graph.
Display DOS: Specify the type of the phonon density of states that will be displayed. Available options
are:
Full
Partial
Note: When atoms are selected in the active structure document, the contribution to the phonon
density of states from only the selected atoms will be plotted. Otherwise, the contribution from all
More...: Provides access to the CASTEP Phonon DOS Analysis Options dialog which allows you to specify
parameters that control the density of states integration method and DOS normalization scheme.
Note: The DOS display and More options are enabled only if Show DOS is checked.
View: Displays the phonon dispersion using the options specified.
Access methods
Menu Modules | CASTEP | Analysis | Phonon

dispersion
Toolbar | Analysis | Phonon dispersion
Phonon density of states selection

The following options are available when Phonon density of states is selected from the list of properties.
Results file: Select the CASTEP results file from which the phonon density of states information will be
taken. When more than one set of results is available, use the button to browse the current
Display DOS: Specify the type of the phonon density of states that will be displayed. Available options
are:
Full
Partial

Note: When atoms are selected in the active structure document, the contribution to the phonon
density of states from only the selected atoms will be plotted. Otherwise, the contribution from all
Units: Specify the frequency units to be used for the phonon dispersion graph. Available options are:
THz
meV
cm-1
More...: Provides access to the CASTEP Phonon DOS Analysis Options dialog which allows you to specify
parameters that control the density of states integration method.
View: Displays the phonon density of states using the options specified.
Access methods

density of states
Toolbar | Analysis | Phonon density of
states
CASTEP Phonon DOS Analysis Options dialog

The CASTEP Phonon DOS Analysis Options dialog allows you to specify the parameters that control the
phonon density of states integration method.
Integration method: Select the method to be used for integrating the density of states results from the
dropdown list. Supported methods are:
Smearing - Gaussian broadening is applied to the eigenvalues obtained from the CASTEP calculation.
Interpolation - eigenvalues (and partial weights for a partial density of states) from the CASTEP
calculation are interpolated onto a finer k-point grid.
The Interpolation method provides an improved representation of the density of states. However, it can
only be used when eigenvalues are available on a 3 × 3 × 3 or larger Monkhorst-Pack grid. If the
Interpolation method cannot be used for the selected results, it will be absent from the dropdown list.
Smearing width: Specify the Gaussian broadening to be used.
Note: This option is enabled only if the Smearing Integration method is selected.
Accuracy level: Specify the quality of the interpolation to be used. Available options are:
Coarse - Interpolates onto a k-point grid of about 50 × 50 × 50.
Medium - Interpolates onto a k-point grid of about 100 × 100 × 100.
Fine - Interpolates onto a k-point grid of about 200 × 200 × 200.
Instrument broadening: Specify an additional broadening to be applied to the interpolated density of
states.
Note: The Accuracy level and Instrument broadening options are enabled only if the Interpolation
integration method is selected.
Normalization: Select the required normalization scheme from the dropdown list. Available options are:

1 - the integral of the generated density of states is 1.

3N - the integral of the generated density of states is the total number of vibrational degrees of
freedom.
Access methods

Density of states | More...
Toolbar | Analysis | Phonon Density of
states | More...
Population analysis selection

The following options are available when Population analysis is selected from the list of properties.
Results file: Select the CASTEP results file from which the population analysis information will be taken.
Assign charges to structure: Imports the selected charges into the active structure document and
assigns them to each atom. You can see the charges by labeling the atoms according to their charge.
Select the type of charges that you wish to import from the dropdown list, available options are:
Mulliken
Hirshfeld
Assign spins to structure: Imports the selected spins into the active structure document and assigns
them to each atom. You can see the spins by labeling the atoms according to their spin. Select the type
of spins that you wish to import from the dropdown list, available options are:
Mulliken
Hirshfeld
Assign Mulliken bond orders to structure: Imports Mulliken bond orders into the active structure
document and assigns them to each bond.
Access methods
Menu Modules | CASTEP | Analysis |

Population analysis
Toolbar | Analysis | Population analysis
Potentials selection
The following options are available when Potentials is selected from the list of properties.

Results file: Select the CASTEP results file from which the potentials information will be taken. When
more than one set of results is available, use the button to browse the current directory and
Note: The local potential cannot be analyzed for calculations with spin-orbit interaction taken into
account.
Potential field: Indicates the type of potential field to be imported. Currently only SCF local potential is
available.
potential field is imported.
Import: Imports the selected potential field from the CASTEP results file into the current structure
document. If the structure is a slab with a region of vacuum, a Chart document named <seedname>
Potential Profile.xcd is also displayed containing a plot of the potential averaged in the
planes perpendicular to the surface normal. This chart document also contains the value of work
function calculated as a difference between the potential level in a vacuum and the Fermi energy.
Note: When calculating a work function from a periodic slab model, you should ensure that the self-
consistent dipole correction is activated on the SCF tab of the CASTEP Electronic Options dialog.
Access methods

Potentials
Toolbar | Analysis | Potentials
Reaction kinetics selection

Select the Reaction kinetics option on the CASTEP Analysis dialog to display the Reaction kinetics dialog.
Results file: Indicates the document containing the reaction ingredients. This field displays the name of
the active document. You can change the active document by clicking on the desired document window
or by double-clicking on the document name in the Project Explorer.
Note: Reaction kinetics calculation can be performed only if the collection document contains well-
defined reaction ingredients: the reactant(s), the product(s), and the transition state. All the
structures must have Hessians and total energy calculated. Reactant(s) and product(s) systems must
be in the ground state - that is all the eigenfrequencies must be real and non-negative.The transition
state must be a valid saddle point with one and only one imaginary frequency for which eigenvectors
represent the reaction path.
From: To: Specify the temperature range for the output of the calculated rate coefficient.
Apply tunneling correction: When checked, indicates that the reaction rate coefficient will be calculated
taking into account the tunneling correction.
Threshold correction: Specify the value to be added to the DFT reaction threshold. This correction
compensates for the underestimation of reaction barriers at the DFT level of theory.
Note: Vibrational frequencies scaling: Specify the value of the scaling coefficient to be applied to
calculated vibrational frequencies before evaluation of vibrational partition functions.

Note: In some reactions, the transition state may have optical isomers with degeneracy n. These
require the prefactor of the Arrhenius rate to be corrected by a factor n. Materials Studio does not
automatically include this prefactor, users are encouraged to add it to the results study table by
hand.
Calculate: Calculate and display a study table containing rate coefficients for the forward and reverse
reactions.
Note: The prefactor for the modified Arrhenius equation is calculated using T0= 298.15 K as reference
temperature.
Access methods
Menu Modules | CASTEP | Analysis | Reaction

kinetics
Toolbar | Analysis | Reaction kinetics
Raman spectrum selection

The following options are available when Raman spectrum is selected from the list of properties.
Results file: Select the CASTEP results file from which the Hessian (dynamical matrix) and ATP tensor
(Born charges) information will be taken. When more than one set of results are available, use the
button to browse the current directory and appropriate subdirectories for results files.
Function: Specify whether to calculate the Intensity or the Activity of the vibrational mode.
Temperature: If the intensity of the vibrational mode is being calculated set the temperature in Kelvin.
Incident light: If the intensity of the vibrational mode is being calculated specify the wavelength of the
incident light in nm. The default value of 514.5 nm corresponds to a standard Ar laser. Other popular
wavelengths for laser Raman spectrometers include 632.8 nm (He-Ne), 785 nm (diode), and 1064 nm
(Nd:YAG).
Smearing: Specify the type of broadening (Gaussian or Lorentzian) and width to be used. Default
Lorentzian broadening with width = 20.0 cm-1.
Units: Specify the units for the X axis of the spectrum, options are:
meV
THz
cm-1
Reverse wavenumber axis: When checked, indicates that the values on the X axis will decrease from
right to left.
Reverse intensity axis: When checked, indicates that the values on the Y axis will decrease from bottom
to top.
Once a Hessian has been imported, vibrational mode frequencies and, if ATP tensors were calculated,
absorption intensities can be displayed in the form of a list of values or graphically as a vibrational
spectrum using the Vibrational Analysis tool.
View: Displays the selected Raman spectrum.

Access methods
Menu Modules | CASTEP | Analysis | Raman

spectrum
Toolbar | Analysis | Raman spectrum
STM profile selection

The following options are available when STM profile is selected from the list of properties.
Results file: Select the CASTEP results file from which the information required to model the STM profile
will be taken. When more than one set of results is available, use the button to browse the current
Note: STM analysis is only available if orbitals were requested.
Note: When more than one set of results is available, it is preferable to use output files for DOS
calculation, especially when STM images of empty bands are required.
STM bias: Specify the value of the bias for STM modeling. Positive bias corresponds to the imaging of
empty (conduction) states, negative bias to the imaging of occupied (valence) states.
View isosurface on import: When checked, an isosurface will be created automatically when the STM
profile field is imported.
Import: Imports the selected STM profile field from the CASTEP results file into the current structure
document.
Access methods
Menu Modules | CASTEP | Analysis | STM

profile
Toolbar | Analysis | STM profile
Structure selection
The following options are available when Structure is selected from the list of properties.
Results file: Select the CASTEP results file from which the structure information will be taken. When
more than one set of results is available, use the button to browse the current directory and
Update structure from CASTEP output: Restores atomic coordinates and cell parameters from the
CASTEP results file.
Note: This button is enabled only if the current document contains a structure for which CASTEP
results are available.
Create trajectory: Creates a trajectory (.xtd) file from the results of a CASTEP Geometry Optimization,
Dynamics or TS Search task.

Note: This button is enabled only if the current document contains a structure for which CASTEP
trajectory results are available.
Access methods

Structure
Toolbar | Analysis | Structure
Thermodynamic properties selection

The following options are available when Thermodynamic properties is selected from the list of
properties.
Results file: Select the CASTEP results file from which the information about phonon frequencies will be
taken in order to evaluate thermodynamic properties. When more than one set of results is available,
use the button to browse the current directory and appropriate subdirectories for results files.
Note: Thermodynamic calculations can be performed only if the system is in the ground state, that is,
geometry optimization is fully converged. This means that all the phonon eigenfrequencies must be
real and non-negative.
From: To: Specify the temperature range for the output of the calculated thermodynamic properties.
Tip: The lower limit should be no less than be 5 K to avoid numerical noise due to inadequate Brillouin
zone sampling at low temperatures. The upper limit should not be significantly greater than the
Debye temperature because of the limited accuracy of the quasiharmonic approximation at high
temperatures.
Plot Debye temperature: When checked, indicates that a separate chart with the temperature
dependence of the Debye temperature will be displayed.
Assign temperature factors to structure: Adds temperature factor information to the structure.
View: Displays the thermodynamics properties using the options specified.
Note: Thermodynamic calculations performed only at the Γ-point give very poor results, as no
acoustic degrees of freedom can be taken into account.
Note: Heat capacity is measured in calories per unit cell per Kelvin. The unit cell can contain several
formula units.
Access methods

Thermodynamic properties
Toolbar | Analysis | Thermodynamic
properties

Results file selector

The Results file selector dialog allows you to browse CASTEP results (.castep) files in the current directory
and appropriate subdirectories and select the file you wish to use as the source of data for analysis of
the chosen property.
Choose results file: Select the results file you wish to use as the source of data for analysis of the chosen
property.
All CASTEP results files that are relevant to the current document and that contain results for the chosen
property will be displayed.
OK: Updates the file selection on the CASTEP Analysis dialog and closes this dialog.
Cancel: Closes the dialog without updating the selection.

Chapter 6: CASTEP keywords
A wide range of input keywords and data blocks are recognized by CASTEP, including some that are not
accessible from the CASTEP setup dialogs.
Tip: For information on CASTEP keywords, refer to the Materials Studio Online Help.

Appendix I: CASTEP References
A list of papers published using CASTEP can be found at the Materials Studio website:
http://3dsbiovia.com/products/collaborative-science/biovia-materials-studio/references/castep-
references/index.html.
Aarons, J. "A New CASTEP and ONETEP Geometry Optimiser",
http://www.hector.ac.uk/cse/distributedcse/reports/castep-geom/castep-geom/HTML/dCSE_
project.html.
Ackland, G.J. "Embrittlement and the Bistable Crystal Structure of Zirconium Hydride", Phys. Rev. Lett.,
80, 2233-2236 (1998).
Ackland, G.J.; Warren, M.C.; Clark, S. J. "Practical methods in ab initio lattice dynamics", J. Phys.:
Condens. Matter, 9, 7861-7872 (1997).
Adamo, C.; Barony V., "Toward reliable density functional methods without adjustable parameters: The
PBE0 model", J. Chem. Phys., 110, 6158-6170 (1998).
Al Allak, H. M.; Clark, S. J. "Valence-band offset of the lattice-matched Β-FeSi2(100)/Si(001)
heterostructure", Phys. Rev. B, 63, 033311 (2001).
Alfe, D. "Ab initio molecular dynamics, a simple algorithm for charge extrapolation", Comput. Phys.
Commun., 118, 31-33 (1999).
Ambros-Drachl, C.; Majewski, J. A.; Vogl, P.; Leising, G. "First-principles studies of the structural and
optical properties of crystalline poly(para-phenylene)", Phys. Rev. B, 51, 9668-9676 (1995).
Ambrosetti, A.; Reilly, A. M.; DiStasio Jr., R. A.; Tkatchenko, A. "Long-range correlation energy calculated
from coupled atomic response functions", J. Chem Phys., 140, 18A508 (2014).
Amin, A.; Newnham, R.E.; Cross, L.E.; Cox, D.E. "Phenomenological and structural study of a low-
temperature phase transition in the PbZrO3 - PbTiO3 system", J. Solid State Chem., 37, 248-255 (1981).
Andersen, H. C. "Molecular dynamics simulations at constant pressure and/or temperature", J. Chem.
Phys., 72, 2384-2393 (1980).
Anderson, O. L. "A simplified method for calculating the Debye temperature from elastic constants", J.
Phys. Chem. Solids, 24, 909-917 (1963).
Anisimov, V. ; Zaanen, J.; Andersen, O.K. "Band theory and Mott insulators: Hubbard U instead of
Stoner I", Phys. Rev. B, 44, 943 (1991).
Arias, T.; Payne, M. C.; Joannopoulos, J. D. "Ab initio molecular dynamics: Analytically continued energy
functionals and insights into iterative solutions", Phys. Rev. Lett., 69, 1077-1080 (1992).
Asahi, R.; Mannstadt, W.; Freeman, A. J. "Optical properties and electronic structures of
semiconductors with screened-exchange LDA", Phys. Rev. B, 59, 7486-7492 (1999).
Ashcroft, N. W.; Mermin, N. D. Solid State Physics, Saunders College: Philadelphia (1976).
Bachelet, G. B.; Hamann, D. R.; Schluter, M. "Pseudopotentials that work: From H to Pu", Phys. Rev. B,
26, 4199-4228 (1982).
Bartók, A. P.; Yates, J. R. "Regularized SCAN functional",J. Chem. Phys. ,150, 161101 (2019).
Baroni, S.; de Gironcoli, S.; dal Corso, A.; Giannozzi, P. "Phonons and related crystal properties from
density-functional perturbation theory", Rev. Mod. Phys., 73, 515-562 (2001).
Baroni, S.; Giannozzi, P.; Testa, A. "Green's function approach to linear response in solids", Phys. Rev.
Lett., 58, 1861-1864 (1987).
Barzilai, J.; Borwein, J. M. "2-Point step size gradient methods", IMA J. Numer. Anal., 8, 141-148 (1988).

Becke, A. D. "Density-functional exchange-energy approximation with correct asymptotic behaviour",

Phys. Rev. A, 38, 3098-3100 (1988).
Becke, A. D.; Edgecombe, K. E. "A simple measure of electron localization in atomic and molecular
systems", J. Chem. Phys., 92, 5397-5403 (1990).
Becke, A. D. "Density-functional thermochemistry. III. The role of exact exchange", J. Chem. Phys., 98,
5648-5652 (1993).
Bellaiche, L.; Vanderbilt, D. "Virtual crystal approximation revisited: Application to dielectric and
piezoelectric properties of perovskites", Phys. Rev. B, 61, 7877-7782 (2000).
Birch, F. "Finite strain isotherm and velocities for single-crystal and polycrystalline NaCl at high pressures
and 300 K", J. Geophys. Res., 83, 1257-1268 (1978).
Blöchl, P.E. Phys. Rev. B, 50, 17 953 (1994).
Bonhomme et al. "First-Principles Calculation of NMR Parameters Using the Gauge Including Projector
Augmented Wave Method: A Chemist’s Point of View", Chem. Rev., 112, 5733-5779 (2012).
Born, M.; Huang, K. Dynamical Theory of Crystal Lattices, Oxford University Press: Oxford (1954).
Boyd, R. W. Nonlinear Optics, Elsevier (2003)
Bradley, C. R.; Cracknell, A. P. The Mathematical Theory of Symmetry in Solids, Clarendon Press, Oxford
(1972).
Ceperley, D. M.; Alder, B. J. "Ground State of the Electron Gas by a Stochastic Method", Phys. Rev. Lett.,
45, 566-569 (1980).
Ceperley, D. M.; Alder, B. J. "Ground State of the Electron Gas by a Stochastic Method", Phys. Rev. Lett.,
45, 566-569 (1980).
Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. J.; Refson, K.; Payne, M. C. "First
principles methods using CASTEP", Zeitschrift fuer Kristallographie, 220 (5-6), 567-570 (2005).
Cococcioni, M.; de Gironcoli, S. "Linear response approach to the calculation of the effective interaction
parameters in the LDA+U method", Phys. Rev. B, 71, 035105 (2005).
Cocula, V.; Starrost, F.; Watson, S. C.; Carter, E. A. "Spin-dependent pseudopotentials in the solid-state
environment: Applications to ferromagnetic and antiferromagnetic metals", J. Chem. Phys., 119, 7659-
7671 (2003).
Cohen, R. E.; Gülseren, O.; Hemley, R. J. "Accuracy of equation-of-state formulations", Am. Mineral., 85,
338-344 (2000).
Corso, A.D.; Conte, A.M. "Spin-orbit coupling with ultrasoft pseudopotentials", Phys. Rev. B., 71, 115106
(2005).
Davidson, E.R.; Chakravorty, S. "A test of the Hirshfeld definition of atomic charges and moments",
Theor. Chim. Acta, 83, 319-330 (1992).
Deyirmenjian, V. B.; Heine, V.; Payne, M. C.; Milman, V.; Lynden-Bell, R. M.; Finnis, M. W. "Ab Initio
Atomistic Simulation of the Strength of Defective Aluminum and Tests of Empirical Force Models", Phys.
Rev. B, 52, 15191-15207 (1995).
de Vita, A. Ph.D. Thesis, Keele University, UK (1992).
de Vita, A.; Manassidis, I.; Lin, J. S.; Gillan, M. J. "The energetics of Frenkel defects in Li2O from 1st
principles", Europhys. Lett., 19, 605-610 (1992).
de Walle, C. G. V.; Blöchl, P. E. "First-principles calculations of hyperfine parameters", Phys. Rev. B, 47,
4244 (1993).
Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.; Humphreys, C. J.; Sutton, A. P. "Electron-energy-loss
spectra and the structural stability of nickel oxide: An LSDA+U study", Phys. Rev. B, 57, 1505 (1998).

Flubacher, P.; Leadbetter, A. J.; Morrison, J. A. "The heat capacity of pure silicon and germanium and
properties of their vibrational frequency spectra", Phil. Mag., 4, 273-294 (1959).
Francis, G. P.; Payne, M. C. "Finite Basis Set Corrections to Total Energy Pseudopotential Calculations",
J. Phys.: Condens. Matter, 2, 4395-4404 (1990).
Frantti, J. et al. "Neutron diffraction studies of Pb(ZrxTi1-x)O3 ceramics", Jpn. J. Appl. Phys., Pt. I, 39,
5697-5703 (2000).
Fuggle, J.C., Inglesfield, J.E. (Eds.) "Unoccupied Electronic States", Springer, Berlin (1992).
Gale, J. D.; Rohl, A. L.; Milman, V.; Warren, M. C. "An ab initio study of the structure and properties of
aluminium hydroxide: gibbsite and bayerite", J. Phys. Chem. B, 105, 10236-10242 (2001).
Gao, S-P.; Pickard, C.J.; Payne, M.C.; Zhu, J.; Yuan, J. "Theory of core-hole effects in 1s core-level
spectroscopy of the first-row elements", Phys. Rev. B, 77, 115122 (2008).
Godby, R. W. "Exchange and correlation in solids", Top. Appl. Phys., 69, 51-88 (1992).
Gonze, X.; Allan, D. C.; Teter, M. P. "Dielectric tensor, effective charges, and phonons in a-quartz by
variational density-functional perturbation theory", Phys. Rev. Lett., 68, 3603-3606 (1994).
Gonze, X. "First-principles responses of solids to atomic displacements and homogeneous electric fields:
Implementation of a conjugate-gradient algorithm", Phys. Rev. B, 55, 10337-10354 (1997).
Govind, N.; Petersen, M.; Fitzgerald, G.; King-Smith, D.; Andzelm, J. "A generalized synchronous transit
method for transition state location", Comput. Mater. Sci., 28, 250-258 (2003).
Green, T. F. G.; Yates, J. R. "Relativistic nuclear magnetic resonance J-coupling with ultrasoft
pseudopotentials and the zeroth-order regular approximation", J. Chem. Phys., 140, 234106 (2014).
Hakala, M.; Puska, M. J.; Nieminen, R. M. "First-principles calculations of interstitial boron in silicon",
Phys. Rev. B, 61, 8155-8161 (2000).
Hamann, D. R.; Schluter, M.; Chiang, C. "Norm-Conserving Pseudopotentials", Phys. Rev. Lett., 43, 1494-
1497 (1979).
Hammer, B.; Hansen, L. B.; Norskov, J. K. "Improved adsorption energetics within density-functional
theory using revised Perdew-Burke-Ernzerhof functionals", Phys. Rev. B, 59, 7413-7421 (1999).
Harris, R.K. "Nuclear spin properties and notation", In: Encyclopedia of nuclear magnetic resonance,
Grant, D.M.; Harris, R.K., editors. Chichester: John Wiley & Sons; 5, 3301 (1996).
Hebert, C. "Practical aspects of running the WIEN2k code for electron spectroscopy", Micron, 38, 12-28
(2007).
Henkelman, G.; Jónsson, H. "Improved tangent estimate in the nudged elastic band method for finding
energy paths and saddle points", J. Chem. Phys., 113, 9978 (2000).
Heßelman, A.; Görling, A. "Blindness of the Exact Density Response Function to Certain Types of
Electronic Excitations: Implications for Time-Dependent Density-Functional Theory", Phys. Rev. Lett.,
102, 233003 (2009).
Heyd, J.; Scuseria, G. E.; Ernzerhof, M. "Hybrid functionals based on a screened Coulomb potential", J.
Chem. Phys., 118, 8207-8215 (2003).
Hirata, S.; Head-Gordon, M. "Time-dependent density functional theory within the Tamm-Dancoff
approximation", Chem. Phys. Lett., 314, 291-299 (1999).
Hirshfeld, F. L. "Bonded-Atom Fragments for Describing Molecular Charge Densities", Theoret. Chim.
Acta, 44, 129-138 (1977).
Ho, K. M.; Fu, C. L.; Harmon, B. N. "Vibrational frequencies via total energy calculations - Applications to
transition metals", Phys. Rev. B, 29, 1575-1587 (1984).

Hutter, J. "Excited state nuclear forces from the Tamm-Dancoff approximation to time-dependent
density functional theory within the plane wave basis set framework", J. Chem. Phys., 118, 3928-3934
(2003).
Iniguez, J.; Vanderbilt, D.; Bellaiche, L. "First-principles study of (BiScO3)1-x-(PbTiO3)x piezoelectric
alloys", Phys. Rev. B, 67, 224-107 (2003).
IUPAC, "Notations and conventions in molecular spectroscopy: Part 2. Symmetry notation.", Pure and
Appl. Chem., 69 , 1641-1649 (1997).
Jirak, Z.; Kala, T. "Crystal Structures of Ferroelectric Phases FR(LT)/FR(HT) In PbZr0.75Ti0.25O3 Solid
Solutions and Their Dependence on Temperature", Ferroelectrics, 82, 79-84 (1988).
Joyce, S. A.; Yates, J. R.; Pickard, C. J.; Mauri, F. "A first principles theory of nuclear magnetic resonance -
coupling in solid-state systems", J. Chem. Phys., 127, 204107 (2007).
Joyce, S. A.; Yates, J. R.; Pickard, C. J.; Brown, S. P. "Density Functional Theory Calculations of Hydrogen-
Bond-Mediated NMR J Coupling in the Solid State", J. Am. Chem. Soc., 130, 12663-12670 (2008).
Juan, Y. M.; Kaxiras, E.; Gordon, R. G. "Use of the generalized gradient approximation in
pseudopotential calculations of solids", Phys. Rev. B, 51, 9521-9525 (1995).
Karki, B. B.; Stixrude, L.; Clark, S. J.; Warren, M. C.; Ackland, G. J.; Crain, J. "Structure and elasticity of
MgO at high pressure", Am. Mineral., 82, 51-60 (1997).
Karki, B. B.; Stixrude, L.; Clark, S. J.; Warren, M. C.; Ackland, G. J.; Crain, J. "Elastic properties of
orthorhombic MgSiO3 perovskite at lower mantle pressures", Am. Mineral., 82, 635-638 (1997).
Karki, B. B.; Stixrude, L.; Crain, J. "Ab initio elasticity of three high-pressure polymorphs of silica",
Geophys. Res. Lett., 24, 3269-3272 (1997).
Karki, B. B.; Clark, S. J.; Warren, M. C.; Hsueh, H. C.; Ackland, G. J.; Crain, J. "Ab initio elasticity and lattice
dynamics of AgGaSe2", J. Phys.: Cond. Matt., 9, 375-380 (1997).
Kerker, G. "Non-singular atomic pseudopotentials for solid state applications", J. Phys. C, 13, L189-L194
(1980).
Kern, G.; Kresse, G.; Hafner, J. "Ab initio calculation of the lattice dynamics and phase diagram of boron
nitride", Phys. Rev. B, 59, 8551-8559 (1999).
King-Smith, R. D.; Payne, M. C.; Lin, J. S. "Real-space implementation of nonlocal pseudopotentials for
first-principles total-energy calculations", Phys. Rev. B, 44, 13063-13066 (1991).
Kleinman, L.; Bylander, D. M. "Efficacious Form for Model Pseudopotentials", Phys. Rev. Lett., 48, 1425-
1428 (1982).
Koelling, D. D.; Harmon, B. N. "A technique for relativistic spin-polarised calculations", J. Phys. C: Solid
State Phys., 10, 3107-3114 (1977).
Kresse, G.; Furthmuller, J. "Efficient iterative schemes for ab initio total-energy calculations using a
plane-wave basis set", Phys. Rev. B, 54, 11169-11186 (1996).
Krukau, A. V.; Vydrov, O. A.; Izmaylov, A. F.; Scuseria, G. E. "Influence of the exchange screening
parameter on the performance of screened hybrid functionals", J. Chem. Phys., 125, 224106 (2006).
Kunc, K.; Needs, R. J.; Nielsen, O.H.; Martin, R.M. Symmetry and Special Points Program K290 (1985).
Laasonen, K.; Pasquarello, A.; Car, R.; Lee, C.; Vanderbilt, D. "Car-Parrinello molecular dynamics with
Vanderbilt ultrasoft pseudopotentials", Phys. Rev. B, 47, 10142-10153 (1993).
Lee, C.; Yang, W.; Parr, R.G. "Development of the Colle-Salvetti correlation-energy formula into a
functional of the electron density", Phys. Rev. B, 37, 785-789 (1988).
Lee, M.H. PhD Thesis, Cambridge University (1996).

Leimkuhler, B.; Noorizadeh, E.; Theil, F. "A Gentle Stochastic Thermostat for Molecular Dynamics", J.
Stat. Phys., 135, 261-277 (2009).
Lejaeghere, K.; Van Speybroeck, V.; Van Oost, G.; Cottenier, S. "Error Estimates for Solid-State Density-
Functional Theory Predictions: An Overview by Means of the Ground-State Elemental Crystals", Critical
Reviews in Solid State and Materials Sciences, 39, 1-24 (2014).
van Lenthe, E.; Baerends, E. J.; Snijders, J. G. "Relativistic total energy using regular approximations", J.
Chem. Phys. , 101, 9783-9792 (1994).
Lin, J. S.; Qteish, A.; Payne, M. C.; Heine, V. "Optimized and transferable nonlocal separable ab initio
pseudopotentials", Phys. Rev. B, 47, 4174-4180 (1993).
Lindh, R.; Bernhardsson, A.; Karlström, G.; Malmqvist, P.-A. "On the use of a Hessian model function in
molecular geometry optimizations", Chemical Physics Letters, 241, 423-428 (1995).
Lloyd-Williams, J. H.; Monserrat, B. "Lattice dynamics and electron-phonon coupling calculations using
nondiagonal supercells", Phys. Rev. B, 92, 184301 (2015).
Louie, S. G.; Froyen, S.; Cohen, M. L. "Nonlinear ionic pseudopotentials in spin-density-functional
calculations", Phys. Rev. B, 26, 1738-1742 (1982).
Makov, G.; Payne, M. C. "Periodic boundary conditions in ab initio calculations", Phys. Rev. B, 51, 4014-
4022 (1995).
Marlo, M.; Milman, V. "Density-functional study of bulk and surface properties of titanium nitride using
different exchange-correlation functionals", Phys. Rev. B, 62, 2899-2907 (2000).
Marzari, N.; Vanderbilt, D.; Payne, M. C. "Ensemble density-functional theory for ab initio molecular
dynamics of metals and finite-temperature insulators", Phys. Rev. Lett., 79, 1337-1340 (1997).
Mazzi, F.; Galli, E.; Gottardi, G. "The crystal structure of tetragonal leucite", Am. Miner., 61, 108-115
(1976).
Milman, V.; Payne, M. C.; Heine, V.; Needs, R. J.; Lin, J. S. "Free energy and entropy of diffusion by ab
initio molecular dynamics: Alkali ions in silicon", Phys. Rev. Lett., 70, 2928-2931 (1993).
Milman, V.; Lee, M. H.; Payne, M. C. "Ground-state properties of CoSi2 determined by a total-energy
pseudopotential method", Phys. Rev. B, 49, 16300 (1994).
Milman, V.; Winkler, B.; White, J. A.; Pickard, C. J.; Payne, M. C.; Akhmatskaya, E. V.; Nobes, R. H.
"Electronic structure, properties and phase stability of inorganic crystals: A pseudopotential plane-wave
study", Int. J. Quantum Chem., 77, 895-910 (2000).
Milman, V.; Warren, M. C. "Elasticity of hexagonal BeO", J. Phys.: Condens. Matter, 13, 241-245 (2001).
Milman, V.; Warren, M. C. "Elastic properties of TiB2 and MgB2", J. Phys.: Condens. Matter, 13, 5585-
5595 (2001b).
Minkiewicz, V. J.; Shirane, G.; Nathans, R. "Phonon Dispersion Relation for Iron", Phys. Rev., 162, 528-
531 (1967).
Miwa, K. "Prediction of Raman spectra with ultrasoft pseudopotentials", Phys. Rev. B, 84, 094304 (2011).
Mohr, P. J.; Taylor, B. N.; Newell, B. D. "CODATA recommended values of the fundamental physical
constants: 2006", Rev. Mod. Phys., 80, 633-730 (2008).
Monkhorst, H. J.; Pack, J. D. "Special points for Brillouin-zone integrations", Phys. Rev. B, 13, 5188-5192
(1976).
Monkhorst, H. J.; Pack, J. D. "Special points for Brillouin-zone integrations" - a reply", Phys. Rev. B, 16,
1748-1749 (1977).
Montanari, B.; Harrison, N. M. "Lattice dynamics of TiO2 rutile: influence of gradient corrections in
density functional calculations", Chem. Phys. Lett., 364, 528-534 (2002).

Mulliken, R. S. J. Chem. Phys., 23, 1833-1846 (1955).

Neugebauer, J.; Scheffler, M. "Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K
adlayers on Al(111)", Phys. Rev. B, 46, 16067-16080 (1992).
Niklasson, A. M. N.; Steneteg, P.; Bock, N. "Extended Lagrangian free energy molecular dynamics", J.
Chem. Phys., 135, 164111 (2011).
Nosé, S. "A molecular dynamics method for simulations in the canonical ensemble", Mol. Phys., 52, 255-
268 (1984).
Nye, J. F. Physical Properties of Crystals, Clarendon: Oxford (1957).
Packwood, D. et al. "A universal preconditioner for simulating condensed phase materials", J. Chem.
Phys., 144, 164109 (2016).
Palik, E. D. Handbook of optical constants of solids, Academic Press: Orlando (1985).
Parrinello, M; Rahman, A. J. Phys. (Paris), C6, 511 (1981).
Parlinski, K.; Li, Z. Q.; Kawazoe, Y. "First-Principles Determination of the Soft Mode in Cubic ZrO2", Phys.
Rev. Lett., 78, 4063-4066 (1997).
Payne, M.C.; Teter, M. P.; Allan, D. C.; Arias, T. A.; Joannopoulos, J. D. "Iterative Minimization
Techniques for Ab Initio Total Energy Calculations: Molecular Dynamics and Conjugate Gradients", Rev.
Mod. Phys., 64, 1045-1097 (1992).
Perdew, J. P.; Zunger, A. "Self-interaction correction to density-functional approximations for many-
electron systems", Phys. Rev. B, 23, 5048-5079 (1981).
Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C.
"Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for
exchange and correlation", Phys. Rev. B, 46, 6671-6687 (1992).
Perdew, J.P.; Burke, K.; Ernzerhof, M. "Generalized Gradient Approximation Made Simple", Phys. Rev.
Lett., 77, 3865-3868 (1996).
Perdew, J.P. et al. "Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces", Phys.
Rev. Lett., 100, 136406 (2008).
Pfrommer, B. G.; Cote, M.; Louie S. G.; Cohen, M. L. "Relaxation of Crystals with the Quasi-Newton
Method", J. Comput. Phys., 131, 233-240 (1997).
Pickard, C. J.; Mauri, F. "All-electron magnetic response with pseudopotentials: NMR chemical shifts",
Phys. Rev. B, 63, 245101 (2001).
Pickard, C. J.; Mauri, F. "First-Principles Theory of the EPR g Tensor in Solids: Defects in Quartz", Phys.
Rev. Lett., 88, 086403 (2002).
Pietrucci, F.; Bernasconi, M.; Di Valentin, C.; Mauri, F.; Pickard, C. J. "EPR g-tensor of paramagnetic
centers in yttria-stabilized zirconia from first-principles calculations", Phys. Rev. B, 73, 134112 (2006).
Porezag, D.; Pederson M. R. "Infrared intensities and Raman-scattering activities within density-
functional theory", Phys. Rev. B, 54, 7830 (1996).
Probert, M. I. J. "Improved algorithm for geometry optimization using damped molecular dynamics", J.
Comput. Phys., 191, 130-146 (2003).
Profeta, M.; Benoit, M.; Mauri, F.; Pickard, C. J. "First-Principles Calculation of the 17O NMR Parameters
in Ca Oxide and Ca Aluminosilicates: the Partially Covalent Nature of the Ca-O Bond, a Challenge for
Density Functional Theory", J. Am. Chem. Soc., 126, 12628-12635 (2004).
Puska, M. J. "Point defects in silicon, first-principles calculations", Comput. Mater. Sci., 17, 365-373
(2000).
Pyykkö, P. "Year-2008 nuclear quadrupole moments", Molecular Physics, 106, 1965-1974 (2008).

Ramer, N. J.; Rappe, A. M. "Virtual-crystal approximation that works: Locating a compositional phase
boundary in Pb(Zr1-xTix)O3", Phys. Rev. B, 62, 743-746 (2000).
Ranganathan, S. I.; Ostoja-Starzewski, M. "Universal Elastic Anisotropy Index", Phys. Rev. Lett., 101,
055504 (2008).
Rappe, A. M.; Rabe, K. M.; Kaxiras, E.; Joannopoulos, J. D. "Optimized pseudopotentials", Phys. Rev. B,
41, 1227-1230 (1990).
Read, A. J.; Needs, R. J. "Calculation of optical matrix elements with nonlocal pseudopotentials", Phys.
Rev. B, 44, 13071-13073 (1991).
Sahl, K. "Refinement of the crystal structure of bicchulite Ca2[Al2SiO6](OH)2", Z. Kristallogr., 152, 13-21
(1980).
Sanchez-Portal, D.; Artacho, E.; Soler, J. M. "Projection of plane-wave calculations into atomic orbitals",
Solid State Commun., 95, 685-690 (1995).
Savin, A.; Jepsen, O.; Flad, J.; Andersen, O. K.; Preuss, H.; von Schnering, H. G. "Electron localization in
solid-state structures of the elements - the diamond structure", Angewandte Chemie-International
Edition , 31, 187-188 (1992).
Segall, M. D.; Pickard, C. J.; Shah, R.; Payne, M. C. "Population analysis in plane wave electronic
structure calculations", Mol. Phys., 89, 571-577 (1996).
Segall, M. D.; Shah, R.; Pickard, C. J.; Payne, M. C. "Population analysis of plane-wave electronic
structure calculations of bulk materials", Phys. Rev. B, 54, 16317-16320 (1996).
Segall, M. D.; Lindan, P. J. D.; Probert, M. J.; Pickard, C. J.; Hasnip, P. J.; Clark, S. J.; Payne, M. C. "First-
principles simulation: ideas, illustrations and the CASTEP code", J. Phys.: Condens. Matter, 14, 2717-
2743 (2002).
Seidl, A.; Gorling, A.; Vogl, P.; Majewski, J. A.; Levy, M."Generalized Kohn-Sham schemes and the band-
gap problem", Phys. Rev. B, 53, 3764-3774 (1996).
Shih, B-C.; Yates , J.R. "Gauge-including projector augmented-wave NMR chemical shift calculations with
DFT+U", Phys. Rev. B, 96, 045142 (2017).
Srivastava, G. P.; Weaire, D. "The theory of the cohesive energies of solids", Adv. Phys., 26, 463-517
(1987).
Steneteg, P.; Abrikosov, I.A.; Weber, V.; Niklasson, A.M.N. "Wavefunction extended Lagrangian Born-
Oppenheimer molecular dynamics", Phys. Rev. B, 92, 075110 (2010).
Sun, J.; Remsing, R. C.; Zhang, Y. ; Sun, Z.; Ruzsinszky, A.; Peng ,H.; Yang, Z. ; Paul, A. ; Waghmare, U.
;Wu, X. ;Klein, M. L. ; Perdew, J. P. Nat. Chem. 8 , 831 (2016).
Tersoff, J.; Hamman, D. R. "Theory of the scanning tunneling microscope", Phys. Rev. B, 31, 805-813
(1985).
Tian, Y.; Xu, B.; Zhao, Z. "Microscopic theory of hardness and design of novel superhard crystals", Int. J.
Refr. Met. Hard Mater., 33, 93-106 (2012).
Troullier, N.; Martins, J. L. "Efficient pseudopotentials for plane-wave calculations", Phys. Rev. B, 43,
1993-2006 (1991).
Tuckerman, M. E.; Liu, Y.; Ciccotti, G.; Martyna, G. J. "Non-Hamiltonian molecular dynamics:
Generalizing Hamiltonian phase space principles to non-Hamiltonian systems", J. Chem. Phys., 115,
1678-1702 (2001).
Vanderbilt, D. "Soft self-consistent pseudopotentials in a generalized eigenvalue formalism", Phys. Rev.
B, 41, 7892-7895 (1990).
Walker, D. et al. "Halite-sylvite thermoelasticity", Am. Mineral., 89, 204-210 (2004).

Warren, J. L.; Worlton, T. G. "Improved version of group-theoretical analysis of lattice dynamics", Comp.
Phys. Commun., 8, 71-84 (1974).
Warren, M. C.; Ackland, G. J. "Ab Initio Studies of Structural Instabilities in Magnesium Silicate
Perovskite", Phys. Chem. Miner., 23, 107-118 (1996).
Warren, M. C.; Ackland, G. J.; Karki, B. B.; Clark, S. J. "Phase Transitions in Silicate Perovskites from First
Principles", Mineral. Mag., 62, 585-598 (1998).
Wei, S. Q.; Chou, M. Y. "Phonon dispersions in silicon and germanium from first principles calculations",
Phys. Rev. B, 50, 4859-4862 (1994).
White, J. A.; Bird, D. M. "Implementation of gradient-corrected exchange-correlation potentials in Car-
Parrinello total-energy calculations", Phys. Rev. B, 50, 4954-4957 (1994).
Winkler, B.; Dove, M. T.; Leslie, M. "Static lattice energy minimization and lattice dynamics calculations
on aluminosilicate minerals", Am. Mineral., 76, 313-331 (1991).
Winkler, B.; Milman, V. "Polymorphism of CsI", J. Phys.: Condens. Matter, 9, 9811-9817 (1997).
Winkler, B. "An introduction to 'Computational Crystallography'", Z. Kristallogr., 214, 506-527 (1999).
Winkler, B.; Pickard, C. J.; Segall, M. D.; Milman, V. "Density functional study of charge ordering in Cs2Au
(I)Au(III)Cl6 under pressure", Phys. Rev. B, 63, 14103 (2001).
Winkler, B.; Hytha, M.; Warren, M. C.; Milman, V.; Gale, J.; Shreuer, J. "Calculation of the elastic
constants of the Al2SiO5 polymorphs andalusite, sillimanite and kyanite", Z. Kristallogr., 216, 67-70
(2001).
Winkler, B.; Pickard, C. J.; Milman, V. "Applicability of a quantum mechanical "virtual crystal
approximation" to study Al/Si-disorder", Chem. Phys. Lett., 362, 266-270 (2002).
Wu, Z.; Cohen, R. E. "More accurate generalized gradient approximation for solids", Phys. Rev. B, 73,
235116 (2006).
Yanson, I. K. "Point contact spectroscopy of metals", Phys. Script., T23, 88-94 (1988).
Yates, J. R.; Pickard, C. J.; Mauri, F. "Calculation of NMR chemical shifts for extended systems using
ultrasoft pseudopotentials", Phys. Rev. B, 76, 024401 (2007).
Yates, J. R."Prediction of NMR J-coupling in solids with the planewave pseudopotential approach",
Magnetic Resonance in Chemistry, 48, S23-S31 (2010).
Yeh, I-C; Berkowitz, M.L. "Ewald summation for systems with slab geometry", J. Chem Phys., 111, 3155-
3162 (1999).
Yin, M. T.; Cohen, M. L. "Theory of lattice dynamical properties of solids - Application to Si and Ge",
Phys. Rev. B, 26, 3259-3272 (1982).

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CASTEP GUIDE

MATERIALS STUDIO 2020

Acknowledgments and References

Dassault Systèmes Customer Support

Setting up SCF parameters 22 Requesting electronic excitations (TD-

Materials Studio 2020 • CASTEP Guide | Page i

Requesting orbital analysis 44 Displaying optical properties 71

Page ii | Materials Studio 2020 • CASTEP Guide

CASTEP file formats - ELF 89 CASTEP

Materials Studio 2020 • CASTEP Guide | Page iii

Formulation of electron localization Quasiparticles and the DFT bandgap 140

Page iv | Materials Studio 2020 • CASTEP Guide

Density of states selection 185 CASTEP Phonon DOS Analysis Options

Materials Studio 2020 • CASTEP Guide | Page v

Materials Studio 2020 • CASTEP Guide | Page 1

Page 2 | Materials Studio 2020 • CASTEP Guide

CASTEP Energy task

1 eV 0.0367493254 Ha 23.0605 kcal/mole 96.4853 kJ/mole

CASTEP Geometry Optimization task

Materials Studio 2020 • CASTEP Guide | Page 3

Figure 1. Experimental vs. CASTEP calculated lattice parameters

Equation of state calculation

Page 4 | Materials Studio 2020 • CASTEP Guide

V0 is the equilibrium volume

Geometry optimization methods

CASTEP Dynamics task

Selecting the thermodynamic ensemble

Defining the time step

Materials Studio 2020 • CASTEP Guide | Page 5

Constraints during dynamics

CASTEP Elastic Constants task

CASTEP Transition State Search task

Page 6 | Materials Studio 2020 • CASTEP Guide

Synchronous transit methods

Materials Studio 2020 • CASTEP Guide | Page 7

Page 8 | Materials Studio 2020 • CASTEP Guide

Modeling disorder in solids

Materials Studio 2020 • CASTEP Guide | Page 9

Setting up CASTEP calculations

Page 10 | Materials Studio 2020 • CASTEP Guide

Setting electronic options

Materials Studio 2020 • CASTEP Guide | Page 11

Quality Express Coarse Medium Fine Ultra-Fine

Page 12 | Materials Studio 2020 • CASTEP Guide

Materials Studio 2020 • CASTEP Guide | Page 13

Setting system parameters

Page 14 | Materials Studio 2020 • CASTEP Guide

To set up a spin-polarized calculation with a specified ordering of atomic moments

Materials Studio 2020 • CASTEP Guide | Page 15

Nonlocal exchange-correlation functionals

Page 16 | Materials Studio 2020 • CASTEP Guide

Several approximations for nonlocal exchange-correlation functionals are available:

Materials Studio 2020 • CASTEP Guide | Page 17

Page 18 | Materials Studio 2020 • CASTEP Guide

Nonlinear core corrected pseudopotentials