A Modified Thomas-Fermi Approximation With Applications

TL;DR

This paper introduces a modified density functional theory based on the Thomas-Fermi approximation, improving accuracy near nuclei and enabling detailed calculations of ion cores, ionization potentials, and band structures for semiconductors.

Contribution

It develops a new DFT approximation that corrects the electron density near nuclei and separates core and valence electrons, facilitating efficient electronic structure calculations.

Findings

Accurately calculates ionization potentials for Group III, IV, V elements.

Separates core and valence electron densities effectively.

Calculates band structures of semiconductors with improved precision.

Abstract

In order to obtain a reasonably accurate and easily implemented approach to many-electron calculations, we will develop a new Density Functional Theory (DFT). Specifically, we derive an approximation to electron density, the first term of which is the Thomas-Fermi density, while the remaining terms substantially correct the density near the nucleus. As a first application, this new result allows us to accurately calculate the details of the self-consistent ion cores, as well as the ionization potentials for the outer s-orbital bound to the closed-shell ion core of the Group III, IV and V elements. Next, we demonstrate that the new DFT allows us to separate closed-shell 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 due to the ion core in the core region; the second represents the residual kinetic energy density resulting from the envelopes of the valence electron orbitals. This kinetic energy 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 the valence density. This equation provides the starting point for a large number of electronic structure calculations. Here, we use it to calculate the band structures of several Group IV and Group III-V semiconductors.