11/25/23, 8:34 PM Tight-binding model - Open Solid State Notes

Similarly to the triatomic system case, we formulate the molecular orbital via the LCAO model:

|Ψ⟩ = ∑ ϕ n |n⟩.

We assume only nearest-neighbor hopping −t and an on-site energy E . The coupled 0

Schrödinger equation of the |n⟩ orbital is:

Eϕ n = E 0 ϕ n − tϕ n+1 − tϕ n−1 .

Again, the periodic boundary conditions imply ϕ N

= ϕ0 .

We now have the equations of motion of both phonons and electrons. All that remains is to
solve them.

Key idea for solving these equations

In order to solve the equations of motion, we need to come up with a reasonable guess. If we
take a look at the equations of motion, we see that they are the same for all atoms. To be
specific, the structure of the equations is the same no matter what value of n we choose. Since
these equations define the solutions, we reason that the solutions should also be independent
of the choice of n. As a result, we assume a plane wave solution, also called a plane wave
ansatz, with the same amplitude for each atom. In the case of phonons, we obtain

iωt−ikx n
u n = Ae ,

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and the ansatz for electrons is given similarly by

iEt/ℏ−ikx n
ϕ n = Be .

We wrote x n
= na and we wrote the time-dependent solution of the Schrödinger equation to
emphasize the similarity between the two systems.

We already know that the periodic boundary conditions only allow plane waves with k being a
multiple of 2π/L. In the case of the electron system, periodic boundary conditions give
ϕ0 = ϕN , which results in

ik0 ikN a
1 = e = e .

The above equation defines the allowed values of k:

2πp
k = , withp ∈ Z.
Na

2π 2πnp

We use the quantized values of k in our plane wave ansatz: e ikx n

= e
ip
Na
na
= e
i
N
. We
notice something interesting if we investigate the case of p → p + N . In this case, the plane
2πn(p+N ) 2πnp 2πnp

wave ansatz becomes e i

N
= e
i
N
+i2πn
= e
i
N
, which is exactly the same solution.
Counting the number of inequivalent plane waves, we find exactly N different solutions in total.
All that is left is to find the energy of each solution!

The reason why solutions with different values of k are identical is aliasing: because the plane
wave is only defined at discrete positions, acquiring a phase factor of 2π between two atoms is
equivalent to nothing happening:

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Once again we substitute the plane wave ansatz into the equations of motion:

iEt/ℏ−ikna iEt/ℏ−ikna iEt/ℏ−ik(n+1)a iEt/ℏ−ik(n−1)a

EAe = E 0 Ae − tAe − tAe ,

Again, we are not interested in a trivial solution, hence we assume A ≠ 0 and thus

−ika ika
E = E 0 − te − te = E 0 − 2t cos(ka),

which gives us the dispersion relation below.

We see that the electron dispersion consists of a band of allowed energies

E 0 − 2t < E < E 0 + 2t . That particles occupy bands of allowed energies is why a dispersion
relation is also often called a band structure. Due to the spin degeneracy, each band has 2N
possible states if we consider a system with N atoms.

If each atom contains 2 electrons and a single orbital, all the states in the band must be
occupied by electrons. Because all the available states are occupied, there is always exactly the
same number of electrons moving in the positive direction, as there are in the negative. Hence,
no matter what we do, our system is incapable of conducting electrons, and therefore we have
derived the existence of insulators!

Let us also compare the electron band structure with the free electron model. Focusing on the
dispersion relation close to the band bottom at k = 0 , we approximate the energy as

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2
E ≈ E 0 − 2t + t(ka) .

If we compare this to the dispersion relation E = ℏ

2 2
k /2m of the free electrons model, we
see that the band structure is similar, but the lowest available energy is E 0 − 2t instead of 0,
and the electrons behave as if they had a different mass m ∗
= ℏ
2
/2ta
2
.

Group velocity, effective mass, density of states

(here we only discuss electrons; for phonons everything is the same except for replacing
E = ℏω )

Let us think what happens if we apply an external electric field to the crystal:

The full Hamiltonian of the system is

2
p
H = + U atomic (x) + eEx,
2m

where U atomic is the potential created by the nuclei, and E the electric field.

A typical electric field is much smaller than the interatomic potential, and therefore we can start
by obtaining the dispersion relation E(k) without electric field (by applying the LCAO method),
and then solve

H = E(k) + eEx.

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To derive how particles with an arbitrary dispersion relation move, we recall the Hamilton's
equations for particle velocity v and force F :

dr ∂H (p, r)
v ≡ =
dt ∂p

dp ∂H (p, r)
F ≡ = − .
dt ∂r

Substituting p = ℏk into the first equation we arrive to the expression for the electron group
velocity v ≡ ℏ
−1
∂E/∂k . From the second equation we obtain that the force acting on electron
in a band stays −eE , which in turn gives results in the acceleration

dv ∂v dp
= = F /m.
dt ∂p dt

Comparing this expression with dv/dt = F /m , we arrive to the effective mass:

−1 −1 −1
2 2
∂v ∂ E ∂ E
∗ 2
m ≡ ( ) = ( ) = ℏ ( ) .
2 2
∂p ∂p ∂k

The group velocity describes how quickly electrons with a certain k-vector move, while the
effective mass describes how hard they are to accelerate by applying external force.

By using the dispersion relation we derived earlier, we obtain the effective mass like this:

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Notice that the effective mass can be negative, which implies the electrons accelerate in the
direction opposite to the applied force.

Density of states

The DOS is the number of states per unit energy. In 1D we have

L L
−1
g(E) = ∑ |dk/dE| = ∑ |v|
2π 2πℏ

The sum goes over all possible values of k and spin which have the same energy E. If we are
working in two or more dimensions, we must integrate over the values of k with the same
energy. Also take note that for energies below E 0 − 2t or above E 0 + 2t , there are no values of
k with that energy, so there is nothing to sum over.

Once again, starting from

E = E 0 − 2t cos(ka),

we get

ka = ± arccos[(E − E 0 )/2t],

and

dk ℏ 1
−1
|v| = ℏ = .
dE a √ 2 2
4t − (E − E 0 )

You can get to this result immediately if you remember the derivative of arccosine. Otherwise
you need to go the long way: compute dE/dk as a function of k, express k through E as we
did above, and take the inverse.

We now add together the contributions of the positive and the negative momenta as well both
spin orientations, and arrive to the density of states

L 4 1
g(E) = .
2π a √ 2 2
4t − (E − E 0 )

A quick check: when the energy is close to the bottom of the band, E = E 0 − 2t + δE , we get
g(E) ∝ δE
−1/2
, as we expect in 1D.

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