Enhancing the efficiency of density functionals with a novel iso-orbital indicator

TL;DR

This paper introduces a new iso-orbital indicator for density functional theory that maintains chemical bond recognition while significantly improving computational efficiency and grid convergence, aiding future functional development.

Contribution

A novel iso-orbital indicator is proposed, reducing the need for dense grids and enhancing recognition of tail regions in electron densities, improving density functional accuracy and efficiency.

Findings

Retains ability to identify chemical bonds

Reduces computational grid requirements

Improves recognition in tail regions

Abstract

Due to its efficiency and reasonable accuracy, density functional theory is one of the most widely used electronic structure theories in condensed matter physics, materials physics, and quantum chemistry. The accuracy and efficiency of a density functional is dependent on the basic ingredients it uses, and how the ingredients are built into the functional as a whole. An iso-orbital indicator based on the electron density, its gradients, and the kinetic energy density, has proven an essential dimensionless variable that allows density functionals to recognise and correctly treat various types of chemical bonding, both strong and weak. Density functionals constructed around the iso-orbital indicator usually require dense real-space grids for numerical implementation that deteriorate computational efficiency, with poor grid convergence compromising the improved accuracy. Here, a novel iso-orbital indicator is proposed based on the same ingredients that retains the capability to identify the same chemical bonds while significantly relieving the requirement of dense grids, and giving an improved recognition for tail regions of electron densities. The novel iso-orbital indicator is therefore expected to be the prime choice for further density functional development.