The Lieb-Oxford Lower Bounds on the Coulomb Energy, Their Importance to Electron Density Functional Theory, and a Conjectured Tight Bound on Exchange

TL;DR

This paper discusses the Lieb-Oxford lower bounds on Coulomb energy, their significance in electron density functional theory, and a conjecture for a tight bound on exchange energy applicable to all spin-unpolarized ground states.

Contribution

It reviews the Lieb-Oxford bounds' role in density functional theory and introduces a conjecture for a universal tight bound on exchange energy.

Findings

Lieb-Oxford bounds apply to exact density functionals.

A tight exchange energy bound is conjectured for all spin-unpolarized ground states.

These bounds inform the development of non-empirical density functionals.

Abstract

Lieb and Oxford (1981) derived rigorous lower bounds, in the form of local functionals of the electron density, on the indirect part of the Coulomb repulsion energy. The greatest lower bound for a given electron number N depends monotonically upon N, and the N-> infinity limit is a bound for all N. These bounds have been shown to apply to the exact density functionals for the exchange- and exchange-correlation energies that must be approximated for an accurate and computationally efficient description of atoms, molecules, and solids. A tight bound on the exact exchange energy has been derived therefrom for two-electron ground states, and is conjectured to apply to all spin-unpolarized electronic ground states. Some of these and other exact constraints have been used to construct two generations of non-empirical density functionals beyond the local density approximation: the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and the strongly constrained and appropriately normed (SCAN) meta-GGA.