Electronic Structure Calculations Using the Thomas-Fermi Model

TL;DR

This paper develops a modified Thomas-Fermi approach using WKB methods to calculate electron densities, ionization potentials, and band structures for various materials, simplifying complex electronic structure calculations.

Contribution

It introduces a new Thomas-Fermi based functional for valence energy that depends on low-frequency density, enabling efficient electronic structure calculations.

Findings

Accurate ionization potentials for Group III, IV, V elements.

Successful band structure calculations for zinc-blende and diamond lattices.

Demonstration of core-valence separation and kinetic energy cancellation techniques.

Abstract

Using the Wentzel-Kramers-Brillouin method, we derive a modified form of the Thomas-Fermi approximation to electron density. This new result enables us to calculate the details of the self-consistent ion cores, as well as the ionization potentials for the first s-orbital bound to the closed-shell ion core of the Group III, IV and V elements. Next, we demonstrate a method for separating core electron densities from valence electron densities. When we calculate the valence kinetic energy density, we show that it separates into two terms: the first exactly cancels the potential energy of the ion core in the core region; the second represents the residual kinetic energy density resulting from the valence density alone. Furthermore, we show that the kinetic cancellation and the residual kinetic energy can be derived from a slowly varying envelope approximation for the valence orbitals in the core region. This kinetic cancellation in the core region and the residual valence kinetic energy term allow us to write a functional for the total valence energy dependant only on a low spatial frequency valence density. In the limit, when we can freeze the potential of the closed-shell ion cores, assuming that they are not greatly influenced by the readjustment of the valence electrons, we can minimize the total valence energy with respect to the valence density degrees of freedom. The variation of the valence total energy equation provides the starting point for a large number of atomic, molecular and solid-state electronic structure problems. Here, we use it to calculate the band structures resulting from the self-consistent valence density and potential on the zinc-blende and diamond lattices. We give band structure results for most of the Group III-V, as well as Group IV, materials.