Frank Discussion of the Status of Ground-state Orbital-free DFT

TL;DR

This paper reviews progress and challenges in orbital-free density functional theory, focusing on the development and evaluation of generalized gradient approximation functionals for kinetic energy in molecular systems.

Contribution

It provides a critical discussion of the status of GGA kinetic-energy functionals, analyzing constraints and empirical performance for molecular applications.

Findings

GGA functionals have limitations in accurately modeling kinetic energy.

Near-origin density behavior influences the effectiveness of GGA functionals.

Empirical GGA optimization offers insights into functional constraints and development.

Abstract

F.E. Harris has been a significant partner in our work on orbital-free density functional approximations for use in ab initio molecular dynamics. Here we mention briefly the essential progress on single-point functionals since our original paper (2006). Then we focus on the advantages and limitations of generalized gradient approximation (GGA) non-interacting kinetic-energy functionals. We reconsider the constraints provided by near-origin conditions in atomic-like systems and their relationship to regularized versus physical external potentials. Then we seek the best empirical GGA for the non-interacting KE for a modest-sized set of molecules with a well-defined near-origin behavior of their densities. The search is motivated by a desire for insight into GGA limitations and for a target for constraint-based development.