The tight binding theory for solids is easy to imagine and have a simple intuitive picture of it.

We can
have a physical picture of the electronic interactions in real space. In the tight binding theory one
assumes that the electrons are tightly bounded to the atoms they belong to and there are only weak
interactions between electrons that belong to an atom and the rest of the atoms of the crystal. The
atoms are almost like individual atoms in empty space and only have small overlap between their
wavefunctions. The system is described by a set of non-interacting wavefunctions that obey Fermi
statistics. We start with the single particle Schrödinger equation in the whole lattice: ( ) ( ) HxEx ˆ Ψ =Ψ
(199) Then one assumes that the delocalized wavefunction Ψ(x) in the above equation is approximately
equal to a linear combination of the wavefunctions of isolated atoms each lying in one of the atomic
sites of the lattice under study; in one dimension we have: ( ) ( ) N n n n ψ = αϕ − x xx ∑ (200) The
positions of the atomic sites n x (look at figure () below) are: n x na = (201) The positions of the atoms
have the linear property (look at figure () below); that is for two vectors n x and mx in the lattice: n m ( )
n m x x na ma n m a x ± =± =± = ± (202) The atomic wavefunctions aren’t necessarily orthonormal, but
we can make them orthonormal. They overlap integrals between the atomic wavefunctions are often
neglected. We assume here that they are orthonormal and we start with the following relation: ( ) ( ) * n
m nm ϕ − ϕ − =δ x x x x dx ∫ (203) 45 The wavefunction must be of the Bloch form as we have seen for
periodic potentials in the section (2.3); that is it must satisfy: ( ) ( ) ikxm ψ+ = ψ xx e x m (204) Let us use
equation (200) to write the translated function ψ + (x xm ) in space in terms of the atomic
wavefunctions; we get: ( ) ( ) ( ( )) N N n n ψ + = αϕ − + = αϕ − − xx xx x x x x m ∑ ∑ n n n m n m (205) If
we make the substitution snm nsm = − ⇒ =+ and use the linear property from equation (202); we get the
following: ( ) ( ) N s m s m s x x x x + ψ+ = αϕ− ∑ (206) Putting the expression above into equation (204);
then we get: ( ) ( ) ( ) ( ) ( ) m m m N s m s N N s s m s ikx ikx ikx s s s s x x x x ee e x x x x x + ψ+ = αϕ− = ψ
= αϕ − = αϕ − ∑ ∑ ∑ (207) From equation we can find the recurrence relation: ikxm sm s e α α + = (208)
The solution for the recurrence relation above is given by: ikxm m 0 α α = e (209) In order to find 0 α ;
we use the probability requirement that the inner product of the delocalized wavefunction over the
whole space is equal to one: ( ) ( ) ( ) ( ) N * * n,m 1 N N 2 2 2 m n nm n,m 1 n,m 1 * n m n m ikx ikx 0 0 0
1 x x dx x x x x dx e 1 N = = = − =ψ ψ = αϕ − ϕ − = α δ =α =α ∑ α ∫ ∫ ∑ ∑ (210) The solution for the
coefficient 0 α then is: 0 1 N α = (211) 46 We can of course multiply the coefficient by a phase in
equation (211), but it does not give any physical meaning since it drops out when we take the absolute
value of 0 α . Finally we have the delocalized function for single electrons in the whole lattice written as
a linear combination of the atomic wavefunctions [10]: ( ) ( ) n N n ik n 1 x x e xx