Tight Binding Project
Tight Binding Project
Tight Binding Project
The project
This project can be carried out using any programming language and is perhaps easiest using
Mathematica or Matlab. It has two parts.
1. Plot the band dispersion relations for electrons on square and hexagonal lattices (graphene).
The objective is to show that for the square lattice the dispersion relations near the band extrema
are parabolic. This is the usual behavior for almost all materials, e.g. Si, Ge etc. In constrast for
Graphene the behavior near the extrema are linear, like in relativistic systems, which motivates a
great deal of interest in studying the electronic properties of graphene. (details are given below)
2. Set up the nearest neighbor tight binding matrices for the square lattice with uniform random
site energies (Anderson model). Diagonalize this matrix using canned routines (e.g. Eigenvalues
in Mathematica). Plot the density of states and the participation ratio (see Eq. (11)) as a function
of the disorder.
If there are more orbitals per site and/or more than one atom per unit cell this expression is ex-
tended in a reasonably straightforward way. Here A N is the normalization constant that is usually
1
1/N 1/2 . It falls out of the band energy calculations and is the band wavefunctions are normalized
at the end, so sometimes it is omitted.
The tight binding method can also be used in cases where there is no lattice periodicity so that
Bloch’s theorem fails. In this more general case the band structure problem requires solution of
large sparse matrices. The general case considers a set of localized orbitals φn and the assumption
that the wavefunction of the system is a linear combination of atomic orbitals (LCAO),
The orbitals φn are call the basis set while cn are the coefficients of the wavefunction that we would
like to find. Notice that Bloch’s theorem is a special case of LCAO where the wavenumber ~k is a
good quantum number. Now we consider Hψ = Eψ which gives,
∑ cn ( H − E)φn = 0, so that ∑ cn (< m| H |n > −E < m|n >) = 0 = ∑( Hmn − ESmn )cn (3)
n n n
2
the last of Eq. (), we find (for all n),
e + 2tcos(ka)
[e + t(e−ika + eika ) − E − sE(e−ika + eika )]eikna = 0; so that Ek = (4)
1 + 2scos(ka)
Because we want the wave function to be single valued, periodic boundary conditions imply that
eik( N +1)a = eika , so that k = 2πl/N, with l an integer. There is a different eigenvalue for each k and
a total of N eigenvalues for an N atom system.
Generalization of the approach above to Hypercubic lattices is straightforward. We just intro-
duce analogous terms in the other directions, so that for example on a cubic lattice the bands are
given by,
Extension to the cases where there are more than one atom per unit cell or where more than one
energy level per site is required lead to more interesting extensions. The case of graphene is where
there are two atoms per unit cell and only one orbital is considered, pz that is the non-bonded
orbital of the graphene system. The band structure of Silicon also has two atoms per unit cell and
is quite challenging and there has been a great deal of study using ab-initio methods that usually
grossly underestimate the band gap. A tight binding model that considers four orbitals per site
with parameters taken from experiments does pretty well. In this case the band structure requires
use of Bloch’s theorem to reduce the system to blocks of 8 × 8 that are diagonalized numerically.
In the Anderson model the matrix is still taken to be tridiagonal in one dimension, moreover
we assume that Sm6=n = 0. The only complication is that the site energies ei are drawn from a
random distribution so Bloch’s theorem does not hold. We then have to find the eigenvalues
and eigenvectors of a matrix that has dimensions N × N where N is the number of atoms in the
system. If we wanted to study the effect of disorder on the band structure of Graphene we would
again consider the eigenvalues of an N × N matrix, while for Si it would be 4N × 4N.
Graphene
Graphene has a planar structure where the chemical bonds are due to sp2 orbit als. The re-
maining unbonded p orbital is by convention called the pz orbital and it has π orientation with
3
pz orbitals of other carbon atoms in a graphene sheet. We only include the pz orbital on each site
in the tight binding calculation of the graphene band structure. The covalently bonded orbitals
are much lower in energy and the 3s orbitals are much higher in energy so this is a reasonable
approximation. Graphene has two sites in its unit cell, A and B, as illustrated in Fig. 1 of Reich et
al. These two sites in combination with the basis vectors
√ √
3 1 3 1
~a1 = x̂ + ŷ; ~a2 = x̂ − ŷ (6)
2 2 2 2
(~R j = n1~a1 + n2~a2 ) enable reconstruction of the infinite graphene sheet. For a Bravais lattice we
have ~k ·~a = 2πn
If there are two atoms per unit cell (as for graphene) then Bloch’s theorem becomes,
ψ~k (~r ) = A N ∑ eik· R j [ a~k φ~kA (~r + ~δA − ~R j ) + b~k φ~kB (~r + ~δB − ~R j )] = a~k ψ~kA + b~k ψ~kB
~ ~
(7)
~R j
where ~δA is the vector from the Bravais lattice point to atom A and ~δB is the vector from the
Bravais lattice point to atom B. Multiplying on the left of this equation by the conjugate of ψ~A and
k
integrating gives,
Similarly,
j j ∗ ,S ∗
where Hij =< ψ~i | H |ψ~ > and Sij =< ψ~i |ψ~ > with i, j = A, B. Also HBA = H AB BA = S AB .
k k k k
Writing these equations in matrix form and taking a determinant of the matrix yields Eq. (1) of
Reich et al. (some more details of the derivation are given in Appendix 1).
Tight binding and the Anderson model
Here we make a further approximation and ignore the term < m|n > which is quite a rough
approximation but can be reintroduced relatively easily later. Moreover the tight binding model is
often written in second quantized form which is the usual form that is used in almost all theoretical
papers on the many body problem (see Appendix 2 for background). The band problems we have
4
studied may be written in the form,
where tij is the overlap integral that we use in the calculation and the sum is over all neighbors
considered in the calculation. Here we consider a one band model where there is only one orbital
per site (like our models of Graphene above). In the simplest case, we only consider nearest
neighbors. ei are the atomic energy levels at each site and in the graphene case e is the energy of a
pz orbital. The band structure is found by setting up the tight binding matrix and diagonalizing it
to find the energy levels in the band. We also get the band eigenfunctions or wavefunctions.
The Anderson model considers the effect of disorder on the wavefunctions. If there is disorder
in ei it is the Anderson model, while if we consider disorder in the hopping elements tij it is
called off-diagonal disorder. The key question is whether the wavefunctions become localized as
a function of the disorder. To test this we calculate the participation ratio R for each eigenfunction
defined as,
(∑i |ψi |2 )2
R= (11)
∑i |ψi |4
What behavior of R is expected for fully localized as opposed to fully extended states? Here ψi are
the elements of the normalized wavefunction.
In this project you should set t = 1 and consider diagonal disorder where ei is drawn ran-
domly from a distribution [−W, W ], where W is the width of the distribution. For wavefunctions
near the band edge and band center, plot IPR as a function of W, for square lattices of different size.
5
that lies in the x-y plane. Our localized orbitals are thus pz orbitals on the sites of a honeycombe
lattice.
The localized basis set is φ(~r − ~R j ) where ~R j is the location of the ith atom of the honeycombe
lattice and φ(~r ) is the pz wavefunction. In its simplest form, and the one often used, the tight bind-
ing method is a single electron model where an the l th electron is described by the Hamiltonian,
h̄2 2
2m l ∑
Hl = − ∇ + V (~rl − ~R j ) (12)
i
and the N-electron Hamiltonian is ∑l Hl . In the tight binding method, Hl is broken into two parts
h̄2 2
Hl = − ∇ + V (~rl − ~R j ) + ∑ V (~rl − ~R j ) = Hl0 + δV (13)
2m l j6=l
∑ eik·R φ(~r − ~R j )
~ ~j
ψ~k (~r ) = (14)
~R j
Bloch’s theorem reduces to the requirement that the above wavefunction must be an eigenstate of
the translation operator T~R j = exp[i p̂ · ~R j /h̄]. In Mathematical terms this is just the observation
that periodic systems are solved by a Fourier transform. The complexity here is that the Fourier
transform must include the particular lattice structure that is present in the system. If there are
two atoms per unit cell (as is the case for a honeycombe) then we have,
where
6
where α is A or B. With this assumption we then look for solutions to
Multiplying on the left of this equation by ψ~∗ gives the matrix equation
k
where
β
Hα,β =< ψ~kα (~r )| H |ψ~ (~r ) > (20)
k
β
Sα,β =< ψ~kα (~r )|ψ~ (~r ) > (21)
k
Note that often the latter overlap corrections are often neglected, however in graphene they are
important and need to be kept.
The general expressions for H and S are
∑
~ ~ ~
eik·( Rl − Rm ) < φ~kα (~r + ~δα − ~Rl )| H |φ~ (~r + ~δβ − ~Rk ) >
αβ β
H~ = (22)
k k
~Rm ~Rl
H~ = N ∑ eik· Rl < φ~kα (~r )| H 0 + δV |φ~ (~r + ~δαβ − ~Rl ) >= N (eα s~ + t~ )
αβ ~ ~ β αβ αβ
(23)
k k k k
~Rl
7
where ~δij = ~δj − ~δi , and
∑ ei k · R
~ ~l
< φ~kα (~r + ~δα − ~Rl )φ~ (~r + ~δβ − ~Rk ) >
αβ β
s~ = (24)
k k
~Rl
and
∑ ei k · R
~ ~l
< φ~kα (~r + ~δα − ~Rl )|δV |φ~ (~r + ~δβ − ~Rk ) >
αβ β
t~ = (25)
k k
~Rl
In the case of Graphene the neighbor and next nearest neighbor hopping elements are,
t =< φ A ∗ (~r )|δV |φ B (~r + ~δ3 ) >; tn nn =< φ A ∗ (~r )|δV |φ A (~r +~a1 ) > (26)
and
Creation and annihilation operators are the same as raising and lowering operators, and for a
harmonic oscillator they are defined by,
p p mω 1/2
a = α( x + i ); a † = α ( x − i ); α=( ) (27)
mω mω 2h̄
8
and
[ a, a† ] = 1; [ a, a] = [ a† , a† ] = 0; (27)
and
1
n̂ = a† a; n̂|n >= n|n >; H = (n̂ + )h̄ω (27)
2
with
This formulation can be extended to treat a many body system composed of many harmonic
oscillators that interact. In that case, if there are N harmonic oscillators, and the number represen-
tation of a state gives the number of bosons in each state, that is |n1 , n2 ....n M > for a system with
M single particle energy levels. The creation and annihilation operators obey the relations,
and,
n̂i = ai† ai ; n̂i |n1 ...ni + 1...n M >= ni |n1 ...ni + 1...n M >; (27)
and
ai† |n1 ...ni ...nm >= (ni + 1)1/2 |n1 ...ni + 1...n M >; (27)
ai |n1 ...ni ...n M >= (ni )1/2 |n1 ...ni − 1...n M > (27)
9
These operators act in the state space of many body wavefunctions constructed from single par-
ticle states, for example for a set of Harmonic oscillators, we need to construct a correctly sym-
metrized N harmonic oscillator wavefunction basis set. A state of this type is written in second
quantized form as,
|n1 ....ni ...n M >= ( a†M )n M ..( ai† )ni ...( a1† )n1 |0 > (27)
In field theory, the interactions are often written in real space where they are called field operators.
Creation and annihilation then occurs at a point in space. Nevertheless Boson second quantized
field operators obey the similar commutation relations,
In the case of Fermions, there are two differences: (i) each state can only have one or zero
particles, (ii) the commutators change to anticommutators, so that,
and,
n̂i = ai† ai ; n̂i |n1 ...ni + 1...n M >= ni |n1 ...ni + 1...n M >; (27)
and
ai† |n1 ...ni ...nm >= (−1)Sk δ(ni )|n1 ...ni + 1...n M >; (27)
and
ai |n1 ...ni ...n M >= (−1)Sk δ(ni − 1)|n1 ...ni − 1...n M > (27)
10
where Sk = ∑ij− 1
=1 n j . These operators act in the state space of many body wavefunctions con-
structed from single particle states. In the case of Fermions, the correct wave functions are Slater
determinants, which have the form,
ψ1 (x1 ) ψ2 (x1 ) · · · ψN (x1 )
1 ψ1 (x2 ) ψ2 (x2 ) · · · ψN (x2 )
Ψ ( x1 , x2 , . . . , x N ) = √ .. .. .. . (27)
N! . . .
ψ1 (x N ) ψ2 (x N ) · · · ψN (x N )
|n1 ....ni ...n M >= ( a†M )n M ..( ai† )ni ...( a1† )n1 |0 > (27)
In field theory, Fermion second quantized field operators obey the commutation relations,
To work with these operators, we need to write the quantum Hamilonians that we are inter-
ested in second quantized form. This is relatively straightforward, as we can write a single particle
wavefunction as,
so the second quantized form for the kinetic energy may be written as,
Z
Ô = ∑ ak1 Ok1 ,k2 a†k2 , Ok1 ,k2 = d3 rψk∗1 (~r )O(~r )ψk2 (~r ) (27)
k1 ,k2
Z
V̂ = ∑ a†k1 a†k2 Vk1 ,k2 ,k3 ,k4 ak3 ak3 , Vk1 ,k2 ,k3 ,k4 = d3 rd3 r 0 ψk∗1 (~r )ψk∗2 (~r 0 )V (~r,~r 0 )ψk3 (~r )ψk4 (~r 0 ) (27)
k1 ,k2 ,k3 ,k4
11
Note that the order of the operators must be with the destruction operators to the right so the
vacuum state has zero energy. This form of the Hamiltonian applies to both Fermions and Bosons,
as the commutation (Bosons) and anticommutation (Fermion) relations account for the symmetry
of the particles.
12