Methods for calculating band structure

The computational solid state physics is a very fast growing area of research. Modern methods for calculating the electronic band structure
of solids allow predicting many important properties of solids.

Tight-binding approximation

Tight-binding method uses atomic orbitals as basis wave functions.

Energy band generation occurred by stacking up several atoms together.

To understand the band structure, The approximation which starts from the wave functions of the free atoms is known as the tight
binding approximation or the LCAO (the linear combination of atomic orbitals) approximation.

In general this approximation is quite good to describe the inner electronic shells of atoms and relatively localized bands. However, it is not
very good for the description of the conduction electrons themselves.

This is because the origin of the free electrons is completely different to the nature of the localized atomic states. Nevertheless, using
tight-binding approximation it is possible to reproduce accurately the band structure of many solids including metals. Moreover, it is possible
to describe reasonably well transport properties of metals as well.
The cellular (Wigner-Seitz) method

The cellular method was the earliest method employed in band calculations by Wigner and Seitz. It
was applied with success to the alkali metals, particularly to Na and K.

Within the cellular method, we divide the crystal into unit cells; each atom is centered at the
middle of its cell, as shown in Fig.

Such a cell, known as the Wigner-Seitz (WS) cell, is constructed by drawing bisecting planes
normal to the lines connecting an atom A, say, to its neighbors, and "picking out" the volume
enclosed by these planes. (The procedure for constructing the WS cell is
analogous to that used in constructing the Brillouin zone in k-space.) For Na, which has a bcc
structure, the WS cell has the shape of a regular dodecahedron.

The Schrödinger equation whose solution we seek is

In order to find the solution of Eq., we assume that the electron, when in a particular cell, say
A, is influenced by the potential of the ion in that cell only. The ions in other cells have a negligible
effect on the electron in cell A because each of these cells is occupied, on the average, by another
conduction electron which tends to screen the ion, thereby reducing its potential drastically
The augmented-plane wave (APW)method

The APW method was developed by Slater in 1937. The APW method is based on assuming a muffin-tin potential. The potential is that of a free
ion at the core, and is strictly constant outside the core.

The wave function for the wave vector k is now taken to be

where r0 is the core radius. Outside the core the function is a plane wave because the potential is constant there. Inside the core the function is
atom-like, and is found by solving the appropriate free-atom Schrödinger equation. Also, the atomic function in above eqn is chosen such that
it joins continuously to the plane wave at the surface of the sphere forming the core; this is the boundary condition here.
The pseudopotential method

Pseudopotential method is distinguished by the manner in which the wave function is chosen. We seek a function which
oscillates rapidly inside the core, but runs smoothly as a plane wave in the remainder of the open space of the WS cell.

where φk is a plane-wave-like wave function and φα is an atomic function. The sum over a extends over all the atomic shells
which are occupied. For example, in Na, the sum extends over the 1s, 2s, and 2p shells. The coefficients cα are chosen such that
the function φk, representing a 3s electron, is orthogonal to the core function cα

The function Φk has the features we are seeking:

Away from the core, the atomic functions φα are negligible, and thus Φk ~ φk, a plane wave. At the core, the atomic
functions are appreciable, resulting in rapid oscillations, as shown in Fig

The pseudopotential concept, (a) The actual potential and the corresponding wave function, as seen by
the electron, (b) The corresponding pseudopotential and pseudofunction.
Eigenvalue Equation

What is an Eigen value equation:

Let Ô be an operator which operates on functions of x. Lets denote the eigen functions of Ô as fj(x). The set
of functions fj(x), j = 1,2,3,….

And lets denote the corresponding eigen values of Ô as λj. If we know the operator Ô , we can extract the
eigen functions and eigen values by solving the equation:

Each eigen function fj(x) has one eigen value λj associated with it. i.e. eigen values and eigen functions come in pairs (fj(x),
λj). Typically many solutions to this equation: (f1(x), λ1), (f2(x), λ2), (f3(x), λ3),…..

The Schrodinger equation is the basic equation for obataining the constant energy of atoms, molecules etc…
The Schrodinger equation itself is a eigen value equation with a general form

Understanding the eigen value equations in general useful for understanding the Schrodinger equation, its solutions and its
implications in solid state physics.
Fermi Surface:

In reciprocal lattice, the ground state of N Bloch electrons is constructed is constructed in a similar fashion as that for free
electrons, i.e. by occupying all one-electron energy levels with band energies En(k) less than EF, where EF is determined by
requiring the total number of levels with energies less than EF to be equal to the total number of electrons.

The wave vector k must be confined to a single primitive cell of the reciprocal lattice. When the lowest of these levels are filled
by a specified number of electrons, two quite distinct types of configuration can result:

1. A certain number of bands may be completely filled, all others remaining empty. Because the
number of levels in a band is equal to the number of primitive cells in the crystal (and because each level can
accommodate two electrons (one of each spin), a configuration with a band gap can arise only if the number of
electrons per primitive cell is even.

2. A number of bands may be partially filled. When this occurs, the energy of the highest occupied level, the Fermi energy EF,
lies within the energy range of one or more bands. For each partially filled band there will be a surface in k-space separating the
occupied from the unoccupied levels. The set of all such surfaces is known as the Fermi surface, and is the generalization to
Bloch electrons of the free electron Fermi sphere. The parts of the Fermi surface arising from individual partially filled bands are
known as branches of the Fermi surface. Analytically, the branch of the Fermi surface in the n-th band is that surface in k-space
determined by
En (k) = EF

Thus the Fermi surface is a constant energy surface (surfaces) in k-space.