A basis-set-free reference for the exact exchange-energy density and functional development

Abstract

The exact local exchange-energy density, obtained from the Slater potential of the Hartree-Fock exchange hole, is a central ingredient of Becke's B05 and B13 functionals and of many other local hybrids. It is usually evaluated in a Gaussian basis, so the local quantity retains a pointwise basis-set incompleteness error. We describe here a basis-set-free numerical code that solves the Kohn-Sham problem on real-space grids for atoms, diatomics, and polyatomics, and returns the exact local exchange-energy density together with the density, its derivatives, the kinetic-energy density, and the reverse Becke-Roussel hole quantities. Reconstructed from the published record of Becke's non-public NUMOL code, AXEL reproduces numerical atomic references through krypton, scalar-relativistic uranium orbital energies, and Becke's diatomic spectroscopic constants. We then extend the original local-density numerical framework to generalized-gradient and hybrid functionals. Comparisons with the independent adaptive-multiwavelet code MRChem give sub-millihartree agreement for Hartree-Fock and PBE0. The same calculations agree with large Gaussian-basis references to a similar level of accuracy. Atom-centred eXact Electronic Limit (AXEL) is intended as both a basis-set-free numerical reference and a platform for exchange-hole-based density-functional development.