Korringa–Kohn–Rostoker method

Introduction

All solids in their ideal state are single crystals with the atoms arranged on a periodic lattice. In condensed matter physics, the properties of such solids are explained on the basis of their electronic structure. This requires the solution of a complicated many-electron problem, but the density functional theory of Walter Kohn makes it possible to reduce it to the solution of a Schroedinger equation with a one-electron periodic potential. The problem is further simplified with the use of group theory and in particular Bloch's theorem, which leads to the result that the energy eigenvalues depend on the crystal momentum k and are divided into bands. Band theory is used to calculate the eigenvalues and wave functions.

Many band theory methods have been proposed over the years. Some of the most widely used, such as the electronic structure programs VASP and WIEN2k, make use of approximations so that acceptable accuracy can be achieved with a minimum of computer resources. The KKR method is chosen when the primary goal is high accuracy.

The parameters obtained from reliable band-theory calculations are useful in theoretical studies of problems, such as superconductivity, for which the density functional theory does not apply.

Mathematical formulation

The KKR band theory equations for space-filling non-spherical potentials are derived in books and in the article on multiple scattering theory.

The wave function near site j is determined by the coefficients c l ′ m ′ j . According to Bloch's theorem, these coefficients differ only through a phase factor c l ′ m ′ j = e − i k ⋅ R j c l ′ m ′ ( E , k ) . The c l ′ m ′ ( E , k ) satisfy the homogeneous equations

where M l m , l ′ m ′ ( E , k ) = m l m , l ′ m ′ ( E ) − A l m , l ′ m ′ ( E , k ) and A l m , l ′ m ′ ( E , k ) = ∑ j e i k ⋅ R i j g l m , l ′ m ′ ( E , R i j ) .

The m l m , l ′ m ′ ( E ) is the inverse of the scattering matrix t l m , l ′ m ′ ( E ) calculated with the non-spherical potential for the site. As pointed out by Korringa, Ewald derived a summation process that makes it possible to calculate the structure constants, A l m , l ′ m ′ ( E , k ) . The energy eigenvalues of the periodic solid for a particular k , E b ( k ) , are the roots of the equation det M ( E , k ) = 0 . The eigenfunctions are found by solving for the c l , m ( E , k ) with E = E b ( k ) . By ignoring all contributions that correspond to an angular momentum l greater than l max , they have dimension ( l max + 1 ) 2 .

In the original derivations of the KKR method, spherically symmetric muffin-tin potentials were used. Such potentials have the advantage that the inverse of the scattering matrix is diagonal in l

where δ l ( E ) is the scattering phase shift that appears in the partial wave analysis in scattering theory. The muffin-tin approximation is good for closely packed metals, but it does not work well for ionic solids like semiconductors. It also leads to errors in calculations of interatomic forces.