Article

pubs.acs.org/jchemeduc

Introduction to Density Functional Theory: Calculations by Hand on

the Helium Atom
Kyle A. Baseden and Jesse W. Tye*
Department of Chemistry, Ball State University, Muncie, Indiana 47306, United States
*
S Supporting Information
Downloaded via INDIAN INST OF TECH BANARAS HINDU UNIV VARANASI on August 31, 2019 at 09:30:40 (UTC).

ABSTRACT: Density functional theory (DFT) is a type of electronic structure

calculation that has rapidly gained popularity. In this article, we provide a step-by-
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

step demonstration of a DFT calculation by hand on the helium atom using Slater’s
X-Alpha exchange functional on a single Gaussian-type orbital to represent the
atomic wave function. This DFT calculation is compared and contrasted with a
Hartree−Fock calculation on the same system. This information is accessible by
advanced undergraduate students studying physical chemistry or calculus-based physics.
KEYWORDS: Upper-Division Undergraduate, Graduate Education/Research, Physical Chemistry, Calculator-Based Learning,
Computer-Based Learning, Hands-On Learning/Manipulatives, Theoretical Chemistry, Molecular Modeling, Computational Chemistry,
Laboratory Computing/Interfacing

■ INTRODUCTION
Electronic structure calculations serve an important role in the
more electrons. HF, MP, and CI calculations rely on the
computation of the atomic or molecular wave function, whereas
understanding of chemical structure and reactivity. The release DFT requires computation of the total electron density and
of user-friendly, commercial electronic structure programs has technically does not require a wave function. In practice,
led to increased access to the techniques of computational however, DFT generally uses a wave function to compute some
chemistry by undergraduate students. Unfortunately, these parts of the energy and the electron density to compute other
programs have been both a boon and a curse to the under- parts of the energy. The total electron density and the normal-
standing of electronic structure theories by students. The pro- ized wave function can be interrelated because the total elec-
grams have become so easy to use that novice users may misuse tron density is the absolute value of the square of the
and overextrapolate the output of these programs. Novice normalized wave function divided by the number of electrons.
chemists may not appreciate that fact that approximate Hartree−Fock treats the electron−electron interactions in a
computations can give useful insight into experimental results very approximate way and, therefore, is the least accurate of
if you understand what a particular computation tells you and these four methods.
what it does not. HF theory has a number of well-established shortcomings
Density functional theory (DFT) is a type of electronic and this method alone is generally not accurate enough to study
structure calculation that continues to gain popularity. A deep most chemical reactions.3 MP and CI, which build upon the HF
understanding of DFT is possible for junior and senior under- calculation, provide very accurate electronic energies for small
graduates in physical chemistry courses as well as beginning atoms and molecules when using very large basis sets, but the
graduate students. To the best of our knowledge, all modern methods are too computationally expensive to apply to larger
physical,1 quantum,2 and computational3 chemistry texts lack atoms and molecules. Modern implementations of DFT can
clear illustration of the implementation of density functional provide much higher accuracy than HF calculations at a lower
theory by specific examples. In general, quantum concepts are computational cost. The low computational cost of DFT has
best understood by examining the full treatment of simple led to a steady increase in the use of density functional theory
systems by hand. This technique can give clear insight into the for the study of larger molecules.3,6
manner in which the theory is implemented in programs. This Mathematical Functions and Functionals
Journal has published a number of articles that give step-by-
step details of Hartree−Fock calculations on small atoms and An understanding of mathematical functions and functionals is
molecules4 as well as articles on a range of other aspects of required to understand the basic language of DFT. Functions
computational chemistry.5 take a number as input and yield a number as output. For
Some important types of modern calculations are Hartree− example, eq 1, could take x = 2 as input and yield f(x) = 4 as
Fock (HF), Møller−Plesset perturbation theory (MP) and output. Functionals are functions of functions. Functionals take
configuration interaction (CI), and density functional theory a function as input and yield a number as output. The input for
(DFT) calculations.2,6 The main practical difficulty for all a function is enclosed in parentheses (for example f(x)),
electronic structure theories is the proper treatment of
electron−electron interactions in species that contain two or Published: November 14, 2014
© 2014 American Chemical Society and
Division of Chemical Education, Inc. 2116 dx.doi.org/10.1021/ed5004788 | J. Chem. Educ. 2014, 91, 2116−2123
Journal of Chemical Education Article

whereas the input for a functional is enclosed in square brackets energy and other properties of atoms and molecules. The
(for example F[y]). A very simple functional is the definite meaning of the wave function has been debated since its
integral functional, F[y] that yields the area under any provided inception, since the wave function is not directly observable by
function, y. For example, let us say that we are interested in the experiment. The wave function is the fundamental variable in
area under any general curve, y = f(x), from x = 0 to x = 3. The Hartree−Fock and post-Hartree−Fock calculations. In 1927,
functional, F[y], is then given by eq 2 Max Born interpreted the wave function in a probabilistic
manner. Born showed the probability density determined by
y = f (x) = 2x (1) squaring the absolute value of the amplitude of a wave function
3 yields the probability of the occurrence of a quantum event.9
F[y] = ∫0 f (x ) d x
(2)
Llewellyn Thomas and Enrico Fermi independently pub-
lished atomic calculations that did not require a wave function
The functional F[y] in eq 2 could take the function given in but instead used the electron density as the fundamental
eq 1 as input and yield the output F[2x] = 9. Functionals can variable in Thomas−Fermi (TF) theory in 1927.10−12 Thomas
be defined as either local or nonlocal. A functional is local if the and Fermi made a leap of faith in assuming from the outset that
functional’s value can be computed for small segments of the the total electronic energy of an atom or molecule is a
input curve and then summed to find the total value. Other- functional of the electron density, although they never formally
wise the functional is called nonlocal. A density functional takes proved the existence of such a functional. One attractive feature
the electron density (a function of the position coordinate, r) as of the electron density is that is it experimentally observable,
an input and outputs a number (an energy). Density func- unlike Schrödinger’s wave function. The original Thomas−
tionals can be local or nonlocal. Fermi model included terms to compute the kinetic energy of
Components of the Total Electronic Energy the electrons (ET), the potential energy due to electron−
nuclear attraction (EV), and the potential energy due to
It is often useful to partition the total electronic energy of an
electron−electron repulsion (EJ) from the electron density. The
atom, molecule, or ion, Etot, into the components shown in eq
TF model yields poor quantitative predictions for real atoms
3, where ET is the total kinetic energy of the electrons, Ev is the
and molecules, because it is exact only in the limit of an infinite
total potential energy of the electrons due to their Coulombic
nuclear charge. It most glaring failures are its inability to
attraction to the nuclear center(s), EJ is the total potential
compute the shell structure of atoms and the fact that it
energy due to the average Coulomb repulsion between pairs of
predicts that all molecules are less stable than their constituent
electrons, EX is the total quantum mechanical exchange energy
atoms.7 Because it considers the total energy to be a functional
of the electrons, and Ec is the total correlation energy of the
electrons7 of the electron density, the Thomas−Fermi energy functional
can be considered a forerunner to modern DFT. The TF
Etot = E T + E V + E J + E X + EC (3) kinetic energy functional produced errors of around 10% in the
calculated kinetic energy.7 Over time, several improvements
The EX and EC terms correct for the overly simplistic EJ term, were made to the original TF functional. In 1930, Paul Dirac13
which is based on the average repulsion between electrons. The added a term to describe the exchange energy of the electrons
EJ term does not take into account the correlated motion of (EX), and in 1935, Carl Friedrich von Weizsäcker14 added cor-
electrons. The electrons in an atom or molecule constantly and rection term for the kinetic energy of the electrons (Weizsäcker
instantaneously adjust to avoid one another. The larger EX term correction).7 Even with the additional terms added by Dirac
corrects for the strongly correlated motion of electrons of the and von Weizsäcker the TF functional still yields a bad estimate
same spin and removes nonphysical self-repulsion terms in EJ. of total energy and fails to predict the shell structure of atoms.7
The smaller EC term mainly corrects for the more weakly In 1950, J. C. Slater derived an exchange functional by
correlated motion of electrons of opposite spin. The ET and EJ dimensional analysis that only differed from Dirac’s by a
terms are always positive, whereas the EV, EX, and EC terms are multiplicative constant.7,15
always negative. The calculation of the ET, EV, and EJ terms are Modern DFT has its roots in the work of Pierre Hohenberg,
identical in many implementations of Hartree−Fock and Walter Kohn, and Lu Jeu Sham. Hohenberg and Kohn showed
density functional theory. The EX term is calculated differently that a universal functional for the total electronic energy of an
in HF and DFT. The EC term is completely missing in HF atom, molecule, or ion, Etot[n(r)], can be defined in terms of the
theory but can be included in an approximate way in DFT. The electron density, n(r), and showed that the total electronic
correlation energy is due to the ability of all of the electrons in energy and other observable properties are a functional of n(r).16
an atom or molecule to adjust to avoid the other electrons and They further proved that the input of the exact ground state
it may be defined mathematically as the difference between the electron density into this universal functional yields the global
exact nonrelativistic energy and the Hartree−Fock energy. The minimum value of this energy functional.17 Although the work
Hartree−Fock limit is the most accurate energy attainable
of Hohenberg and Kohn proved that the universal density
without considering electron correlation.
functional must exist, their work does not prescribe the form
Beginnings of Density Functional Theory for this functional nor the way in which the electron density
Schrödinger published his famous equation that predicts be- should be described. The total electronic energy can be written
havior of particles in a quantum system in 1926.8 The as shown in eq 4, where each term is dependent on the total
Schrödinger equation is a partial differential equation that electron density, n(r). The equation developed by Kohn and
shows how a quantum system evolves over time. The central Sham made DFT a practical computational tool.18 The Kohn−
idea of Schrödinger’s theory is that all of the information about Sham equation is the Schrödinger equation of a fictitious
a quantum system is contained in the system’s wave function. system of noninteracting electrons that generate the same
At the very least, Schrödinger’s wave function is a convenient density as the system of interest. This approximation allowed
mathematical construct that can used to calculate the total Kohn and Sham to more accurately compute each electron’s
2117 dx.doi.org/10.1021/ed5004788 | J. Chem. Educ. 2014, 91, 2116−2123
Journal of Chemical Education Article

kinetic energy in terms of Kohn−Sham orbitals in a manner the calculations use atomic units, meaning that distances will be
analogous to HF measured in units of the Bohr radius (a0 = 52.9 pm) and
energies are in units of hartree (or au = atomic units).
Etot[n] = E T[n] + E V [n] + E J[n] + E X [n] + EC[n] (4) Additional activities, including the calculation of the Hartree−
The electron density can be represented using different Fock and X-Alpha atomic orbital energies, are given in the
Supporting Information.

■
several types of mathematical functions.3 The original DFT
calculations were performed using planewave functions as basis CLOSED-SHELL HARTREE−FOCK EQUATIONS
sets. The infinite extent of these functions was ideal for
computations on extended structures such as metal surfaces or Let us first discuss a simple HF calculation first since the
crystalline solids. For calculations of discrete atoms and mole- concept of the exchange energy originated in Hartree−Fock
cules, atom-centered basis sets are generally more appropriate. theory. Equation 7 is the HF equation for computing the total
In this text, the electron density is represented by a single atom- Hartree−Fock energy, EHF tot for any closed-shell system of N
centered Gaussian basis function, χi(r). In general, the electrons.23 For the helium atom (N = 2), the general HF
optimization of the total electron density, n(r), is accomplished equation given in eq 7 greatly simplifies to yield eq 8.
by systematic variation of the linear expansion coefficients, ci, in N /2 N /2 N /2
HF
eq 5 to obtain the lowest possible total energy Etot =2 ∑ haa + ∑ ∑ (2Jab − Kab)
x a=1 a=1 b=1 (7)
n(r ) = (∑ (ci χi (r ))2 HF
(5)
Etot (He) = 2h11 + 2J11 − K11 (8)
i=1

■
The equations consist of some terms that deal with one
STRENGTHS AND WEAKNESSES OF OUR MODEL electron at a time and other terms that deal with two electrons
at a time. The one-electron terms are the kinetic energy of each
We have chosen to use the Kohn−Sham formulation of DFT to electron (Taa) and the Coulombic potential energy of each
compute the total energy of the helium atom, because helium’s electron due to its attraction by the nuclei (Vaa). The Taa and
total energy is accurately known from experiment. The experi- Vaa terms for each electron are generally summed together to
mentally observed total electronic energy of the helium atom is yield a single one-electron term for each electron called the
−2.9034 au.19 The total electronic energy of the He atom is core term, haa. The Jab and Kab terms are the two-electron
determined as the sum of the first and second ionization terms. The Jab terms are the electron−electron Coulomb
energies. repulsion energy terms. These terms are due to the Coulombic
⎛ 2α ⎞3/4 potential energy of the repulsion of each electron with every
φ(r ) = 2⎜ orb ⎟ exp( −αorbr 2) electron in the system (including itself). The Kab terms are
⎝ π ⎠ (6) exchange energy terms. These terms are due to the exchange
A variety of computational methods have been used in the interaction of each electron with every electron in the system
past to calculate the total energy of the helium atom to very with the same spin (including itself). The Kab terms are a
high accuracy.20 Although our computations are not very consequence of the antisymmetric nature of the wave functions
accurate, they highlight many of the procedures used in higher- used for these calculations. The two-electron Jab and Kab terms
level computations and demonstrate the manner in which more change during the optimization of the wave function, whereas
accurate results may be obtained. We will discuss the short- the one-electron haa terms remain constant.
comings of our model. We have represented the 1s orbital of The number of Coulomb and expected exchanged interac-
helium with a single normalized Gaussian type orbital (GTO, tions is easy to illustrate diagrammatically as shown in Figure 1
shown in eq 6). GTO’s are the most common type of orbitals
used in electronic structure calculations. The orbital exponent
coefficient, αorb, determines the rate at which the wave function
and the electron density decrease as a function of increasing
distance from an atomic center.21 A single GTO is a poor
model for the true atomic wave function of helium and its
electron density. We expect that it will yield poor values for the
total electronic energy. The benefit to using a single GTO in
our derivation is that it allows one to analytically integrate the
exchange functional. The sole method of electron density Figure 1. Simple diagram showing the Jab interactions between all
electrons and Kab interactions between electrons of the same spin. ε1
variation and optimization in our calculation is adjustment of and ε2 are the names of the orbitals containing these electron pairs.
the orbital exponent coefficient, αorb. In general practice, com-
putations involve orbitals constructed from a linear combina-
tion of two or more GTO’s in which the orbital exponent for a closed-shell 4-electron system. For this system, one expects
coefficients remain constant, and the linear expansion six Jab terms among the four electrons and one Kab between the
coefficients are optimized. The use of two or more GTO’s two up electrons and one Kab term between the two down
would require us to use numerical integration of the exchange electrons. One can generalize to say that one expects
functional, and we find utility in being able to solve these N-electron system to experience ((N(N − 1))/2) Coulomb
equations analytically. We have chosen to model the exchange interactions and ((N(N − 2))/8) exchange interactions
energy, EX, using the Slater’s X-Alpha exchange functional and between the up electrons ((N(N − 2))/8) between the
to model correlation energy, EC, we will use correlation down electrons. Interestingly, the Jab and Kab summations in
functional (III) from Vosko, Wilk, and Nusair’s paper.22 All of eq 7 lead to more Coulomb and exchange terms than one
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Journal of Chemical Education Article

would expect. For an N-electron system, eq 7 predicts N2/2 The homogeneous electron gas (HEG, also known as the
Coulomb interactions and N2/4 total exchange interactions. uniform electron gas or jellium) is an important theoretical
The N/2 extra Jaa terms are referred to as self-repulsion inter- construct that bears discussion before proceeding further. One
actions and the N/2 extra Kaa terms are referred to as a self- can imagine constructing the HEG by placing N electrons and a
exchange interactions. In HFT, the Jaa and Kaa terms are equal uniformly distributed total positive charge of N+ into a cube of
in magnitude (for the same a), and therefore, the self-repulsion volume, V, so that the net charge within the cube is zero. The
term is completely removed by the self-exchange term. electrons within this cube maintain a uniform electron density
Calculation of the T, V, J, and K Energy Terms since the positive charge is uniformly distributed within the
cube rather than concentrated in nuclei. The potential energy
Thijssen’s text gives the necessary equations for the calculation
of attractions between the electrons and the homogeneous
of the one-electron Tab and Vab terms that compose hab
positive charge (EV) exactly cancels potential energy due to the
as well as the two-electron Jab and Kab terms involving multiple
electron−electron repulsions (EJ). Therefore, the total energy
1s GTO’s on multiple atomic centers.24 We have simplified
of the HEG is simply the sum of the total kinetic energy (ET),
the equations given in Thijssen’s text since we are dealing with
total exchange energy (EX), and total correlation energy (EC).
a single normalized GTO located on a single helium center
The exchange energy per electron for the homogeneous
(Z = 2 for the V term) and these are given as eqs 9−12 below.
electron gas was calculated analytically by Bloch25 (in 1929)
h11 = T11 + V11 (9) and Dirac13 (in 1930) using planewave basis functions.26,27 The
equation for the Hartree−Fock exchange energy can be
1 2 rewritten as a functional of the first order density matrix,
T11 = φ1 ∇ φ1 = +1.5(αorb)
2 (10) which can be approximated as the sum of the squares of the N/
2 occupied orbitals. In the limit of N → ∞, V → ∞ with N/V
2 remaining finite, the sum of over N/2 occupied orbitals is
V11 = φ1 φ replaced by integration over a sphere from 0 to kF =
r 1
(3π2n(r))1/3, where kF is the wavevector of the highest occu-
⎛ 32 ⎞1/2 pied orbital in our system known as Fermi wavevector.
= −⎜ ⎟ (αorb)1/2
⎝π ⎠ Following some tedious math, this result yields the exchange
energy per electron for the HEG.
≈ −3.192(αorb)1/2 (11)
Local Density Approximation Exchange Functional
J11 = K11 The simplest exchange functional is referred to as the local den-
sity approximation (LDA) functional for closed-shell systems.
1 The LDA exchange functional is based on the assumption that
= φ1φ1 φφ
r 1 1 the exchange energy density at every position in space for an
atom or molecule can be modeled as the exchange energy
⎛ 4 ⎞1/2
= ⎜ ⎟ (αorb)1/2 density of the HEG having the same density that is found at that
⎝π ⎠ position. To be entirely clear, invoking the uniform electron gas
≈ +1.128(αorb)1/2 as the source of the exchange energy functional is not
(12)
equivalent to assuming that the electron density of the atom

■ CLOSED-SHELL DFT EQUATIONS

The closed shell DFT equations for an N-electron system are
or molecule is a constant throughout space.
The exchange energy per electron, εHEGX , has been computed
for the HEG and is given in eq 15. Because the total electron
simple to derive from the corresponding closed-shell HF density is the number of electrons per unit volume, multi-
equations. The sum of Kab terms in the HF equation for the plication of εHEG
X by the total electron density yields the ex-
total electronic energy is replaced by the total exchange energy change energy per unit volume (EX/V). Integration over all
term, EX, to yield the DFT computed total electronic energy, space (dτ = 4πr2 dr in spherical coordinates) yields the total
EDFT
tot as shown in eq 13. The summations in eq 13 are over one
exchange energy of the system, which is shown in eq 16. In this
term since helium is a two-electron system (N = 2). The gen- text, we will use Slater’s X-Alpha functional15 for calculation of
eral DFT equations given in eq 13 greatly simply to yield eq 14 the exchange energy. Slater’s formulation of an exchange
functional multiplies the LDA equations by an empirical scaling
N /2 N /2 N /2
DFT constant of 1.05 to yield the X-Alpha equations for the total
Etot =2 ∑ haa + ∑ ∑ (2Jab ) − Ex exchange energy is given as eq 17
a=1 a=1 b=1 (13)
⎛ 3 ⎞⎛ 3 ⎞1/3
DFT
Etot (He) = 2h11 + 2J11 − Ex (14) εXHEG[n(r )] = −⎜ ⎟⎜ ⎟ (n(r ))1/3
⎝ 4 ⎠⎝ π ⎠ (15)
In DFT, the Jab terms are calculated in the same manner as
∞
HFT, but the sum of Kab terms is approximated by an EX term
using an approximate density functional. Because the EX term in
E XLDA = −(4π ) ∫0 (r 2)(εXHEG)(n(r )) dr
DFT calculations is approximate, it may not completely remove the ⎛ 3 ⎞⎛ 3 ⎞1/3 ∞
energy from self-repulsion Jaa terms. Therefore, DFT computed = −⎜ ⎟⎜ ⎟ (4π )
⎝ 4 ⎠⎝ π ⎠ ∫0 (r 2)(n(r ))4/3 dr
(16)
energies may reflect some unremoved self-repulsion energy.
Homogeneous Electron Gas
⎛ 3 ⎞⎛ 3 ⎞1/3 ∞
The exchange and correlation energy density functionals can E XXα = −1.05⎜ ⎟⎜ ⎟ (4π )
⎝ 4 ⎠⎝ π ⎠ ∫0 (r 2)(η(r ))4/3 dr
(17)
only be determined accurately for very simple model systems.
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Correlation Functionals exchange energy is the exact exchange energy for the single
There is no analytical expression for the correlation energy at determinant wave function that yields the minimum total
the intermediate electron densities generally observed in atoms energy from the Hartree−Fock equation. It does not mean
and molecules. The correlation energy per electron can be that the value of the Hartree−Fock exchange is the correct
solved exactly at the limits of very low and very high electron amount of exchange energy for an atom or molecule using any
density, but the expression for the intermediate electron den- other theory. Some early attempts at calculating accurate total
sities present in atoms and molecules is unknown. In 1980, energies using DFT attempted to develop a correlation
Ceperley and Alder performed accurate quantum Monte Carlo functional as an add-on for HF calculations. Those correlation
simulations on the HEG at intermediate densities.28 Various functionals performed much more poorly when compared to
researchers have proposed equations to estimate the correlation experimental data than calculations in which both the exchange
energy per electron at intermediate electron densities by and correlation functionals had been developed in tandem. The
extrapolation of the between the low density and high-density central issue is that fact that the wave function has a different
limits or based on the work of Ceperley and Alder.6 meaning in these two theories. The optimal wave function in HFT
Calculation of the Total Electron Density and EX
is the wave function that minimizes the HF total energy equation,
whereas the wave function in DFT is the wave function that yields
A normalized GTO for a 1s orbital was given in eq 6. The total the density that minimizes the Kohn−Sham total energy equation.
electron density for this two-electron system is the abso- In order to demonstrate the manner in which the different
lute value of the GTO basis function squared then divided by theories yield different wave functions, we performed a
N (N = 2 for He) to yield eq 18. The four-third root of n(r) is calculation in which we added the VWN correlation functional
easily computed from eq 18 and given in eq 19. The sub- energy to a HF calculation of total energy of the helium
stitution of eq 19 into eq 17 yields a known definite integral.29 atom using a single GTO, which we refer to as HFVWN. The
The use of a table of integrals and simplification of the value of α that minimizes the HFVWN total energy, αHFVWN is
opt
constants yields eq 2030 found to be 0.750,which yields a computed total energy of
⎛ 2α ⎞3/2 −2.4504 au. This value differs from the optimal value for the
n(r ) = 2⎜ orb ⎟ exp( −2αorbr 2) HF calculation, αHFopt = 0.769. The different values of α yield
⎝ π ⎠ (18) different atomic wave functions, and therefore, the use of the
HF exchange energy in this calculation has no theoretical basis.
⎛ 2α ⎞2 ⎛ 8 ⎞
n(r )4/3 = (2)4/3 ⎜ orb ⎟ exp⎜ − αorbr 2⎟ Theory Effects and Basis Set Effects
⎝ π ⎠ ⎝ 3 ⎠ (19)
We have calculated the total electronic energy for the helium
⎛ 317 ⎞1/6 atom using a single GTO by hand (entries 3 and 7 in Table 1)
E XXα = −1.05⎜ 19 5 ⎟ (αorb)1/2 ≈ −1.013(αorb)1/2
⎝2 π ⎠ (20) Table 1. Comparison of Basis Sets and Methods for

■
Calculation of the Total Electronic Energy and Atomic
CALCULATION OF THE TOTAL ELECTRONIC Orbital Energy of Heliuma
ENERGY entry type of data basis set Etot % of HF limit
Using eqs 8, 14, and 9−12, eqs 21 and 22 can be written for the 1 experiment n/a −2.9034 n/a
total energy of the helium atom as a function of the orbital 2 HF limit n/a −2.8617 n/a
coefficient, αorb. The optimal values of αorb yield the minimum 3 HF STO-1G −2.3012 80
total energy for Hartree−Fock and X-Alpha calculations using 4 HF STO-2G −2.7022 94
this basis set. The optimal value of αorb for eqs 21 and 22 can be 5 HF STO-3G −2.8078 98
determined analytically by differentiation of these expressions 6 HF STO-6G −2.8463 99
with respect to αorb. The optimal values for αorb are 0.769 for 7 X-Alpha STO-1G − 2.2008 77
the HF calculation and 0.734 for the X-Alpha calculation. 8 X-Alpha STO-2G −2.5960 91
Substitution of the optimal values into eqs 21 and 22 yield our 9 X-Alpha STO-3G −2.7026 94
computed values for the total electronic energy of the helium 10 X-Alpha STO-6G −2.7413 96
atom, Etot, using each model. We compute values of EHF tot = a
Equations 21 and 22 give values of -2.3021 and -2.2025 au for entries
−2.3012 au from the HF calculation and EXα tot = −2.2008 au 3 and 7 due to rounding of constants.
from the X-Alpha computation. The optimal α value is inversely
related to the size of the orbital. The α value obtained for the as well by a series of computations using the Gaussian 09
X-Alpha computation is smaller because the unremoved self- program using different basis (entries 4−6 and 8−10).31,32 Our
repulsion causes the orbital to expand relative to the HF orbital single GTO basis set is not an accurate representation of the 1s
HF wave function. Better basis sets can be built from a linear
Etot = 2(1.5αorb) − 2(3.192(αorb)1/2 ) + 2(1.128(αorb)1/2 ) combination of GTO’s. Entries 4−6 and 8−10 use STO-nG
− 1.128(αorb)1/2 (21) basis sets in which the 1s atomic orbital is represented by linear
combination of n GTO basis functions.3,33 It is obvious that the
Xα
Etot = 2(1.5αorb) − 2(3.192(αorb)1/2 ) + 2(1.128(αorb)1/2 ) total energies calculated by either method rapidly improve as
quality of the basis set increases. The comparison of entries
− 1.013(αorb)1/2 (22) 3−6 with entries 7−10 shows that in this case the value of
total electronic energy is only slightly better for HF versus the
Hartree−Fock and Exact Exchange X-Alpha method. The HF and X-Alpha computed values for the
The term “exact exchange” is often misused or misunderstood total electronic energy are shown to improve as the number of
in discussions of quantum chemistry. The Hartree−Fock GTO basis functions is increased.34
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Table 2. Computeda Energy Components For Selected Closed-Shell Atoms

atom N ET EV EJ EX Etot %HFb %SICc
He 2 2.7 −6.5 2.1 −0.9 −2.6 90 100
Be 4 14.3 −33.1 7.6 −2.5 −13.6 91 50
Ne 10 121.5 −299.1 67.3 −11.7 −122.1 95 20
Ar 18 491.2 −1197.5 229.0 −28.8 −506.2 96 11
Kr 36 2741.2 −6558.8 1172.1 −93.0 −2738.4 99 6
a
These results were calculated using the X-Alpha method as implemented in Gaussian 09 using the STO-2G basis set in each case. bPercent of HF
exchange energy obtained from the X-Alpha using the same basis set. cPercent of exchange interactions due to self-exchange interactions. It is not the
percentage of the total exchange energy due to self-exchange interactions.

Helium Is the Exception That Proves the Rule

Table 2 illustrates three reasons that the helium atom is the
■ ACKNOWLEDGMENTS
We thank Ball State University for generous start-up funds and
worst-case scenario for density functional theory: (1) The the Center for Computational Nanoscience at Ball State
helium atom has the largest percent of exchange interactions University for computational time and software.

■
due to self-exchange (100%). The percent of Kab terms due to
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