A Density Functional Theory for the Average Electron Energy

Artikel i vetenskaplig tidskrift, 2023

A formally exact density functional theory (DFT) determination of the average electron energy is presented. Our theory, which is based on a different accounting of energy functional terms, partially solves one well-known downside of conventional Kohn-Sham (KS) DFT: that electronic energies have but tenuous connections to physical quantities. Calculated average electron energies are close to experimental ionization potentials (IPs) in one-electron systems, demonstrating a surprisingly small effect of self-interaction and other exchange-correlation errors in established DFT methods. Remarkable agreement with ab initio quantum mechanical calculations of multielectron systems is demonstrated using several flavors of DFT, and we argue for the use of the average electron energy as a design criterion for density functional approximations.