Pair interactions of rare-gas atoms as a test of exchange-energy-density functionals in regions of large density gradients

Daniel J. Lacks and Roy G. Gordon
Phys. Rev. A 47, 4681 – Published 1 June 1993
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Abstract

The exchange energy for pairs of helium and neon atoms was calculated with recently proposed exchange-energy functionals for Hartree-Fock electron densities, and compared with the exact (Hartree-Fock) exchange energy. While all of the functionals calculate the total exchange energies to within 1%, most of the functionals give very poor results for ΔEexc, the exchange-energy contribution to the interaction energy. At the positions of the energy minima for the atom pairs, most functionals give ΔEexc in error by over 100%. The reason for the difference in accuracy between the total exchange energy and ΔEexc is that the total exchange energy is dominated by the high density and small gradient regions near the nuclei, while ΔEexc is dominated by the low density and large gradient regions between the atoms. We propose an exchange functional which gives good results for both the total exchange energy and ΔEexc. We also show that the Lieb-Oxford bound can only be applied globally, and not locally as some investigators have suggested.

  • Received 29 October 1992

DOI:https://doi.org/10.1103/PhysRevA.47.4681

©1993 American Physical Society

Authors & Affiliations

Daniel J. Lacks and Roy G. Gordon

  • Department of Chemistry, Harvard University, Cambridge, Massachusetts 02138

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Issue

Vol. 47, Iss. 6 — June 1993

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