Semi-Local Parameterization of the Electron Localization Function in Second-Order Density Gradients

TL;DR

This paper introduces a new semi-local functional approximation for the electron localization function (ELF) based on second-order density gradients, enabling qualitative analysis of electron localization in systems where only density data is available.

Contribution

It develops a simple, generally applicable ELF approximation using an exactly solvable model, capturing qualitative features without requiring Kohn-Sham orbitals or kinetic energy density.

Findings

Successfully applied to analyze bonds in solid Al and Si

Captured qualitative features of electron localization

Useful for systems with only electron density data

Abstract

The electron localization function (ELF) is a universal measure of electron localization that allows for, e.g., an effective characterization of physical bonds in molecular and solid state systems. In the context of the widely used Kohn-Sham density-functional theory (KS-DFT) and its generalizations, ELF is given in terms of the single-particle electron density as well as the non-interacting kinetic energy density (KED) of the KS system. Starting from the notion of an edge electron gas put forth by Kohn and Mattsson, we here use an \emph{exactly soluble}, strongly correlated few-electron model of a harmonically confined electron gas in order to parameterize the positive-definite non-interacting KS KED in terms of the density and its reduced second-order gradients. We arrive at a simple, yet generally applicable functional approximation to ELF expressed in the electron density and its derivatives. To demonstrate the validity of our approach, we use the obtained parameterization to perform topological analysis of the bonds in solid Al and Si, and to study physical and chemical adsorption of graphene on a Ni surface. We find that while the expression does not provide a quantitatively accurate approximation of absolute ELF values, the most essential qualitative features are captured. Hence, the expression is useful in contexts where the electron density is available, but not the KS orbitals or the KED, and one desires a qualitative picture of the electron localization that mimics ELF.