Asymptotic behavior of the Hartree-exchange and correlation potentials in ensemble density functional theory

Tim Gould*, Stefano Pittalis, Julien Toulouse, Eli Kraisler, Leeor Kronik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

We report on previously unnoticed features of the exact Hartree-exchange and correlation potentials for atoms and ions treated via ensemble density functional theory, demonstrated on fractional ions of Li, C, and F. We show that these potentials, when treated separately, can reach non-vanishing asymptotic constant values in the outer region of spherical, spin unpolarized atoms. In the next leading order, the potentials resemble Coulomb potentials created by effective charges which have the peculiarity of not behaving as piecewise constants as a function of the electron number. We provide analytical derivations and complement them with numerical results using the inversion of the Kohn-Sham equations for interacting densities obtained by accurate quantum Monte Carlo calculations. The present results expand on the knowledge of crucial exact properties of Kohn-Sham systems, which can guide development of advanced exchange-correlation approximations.

Original languageEnglish
Pages (from-to)19805-19815
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume21
Issue number36
DOIs
StatePublished - 2019

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