TY - JOUR
T1 - Asymptotic behavior of the Hartree-exchange and correlation potentials in ensemble density functional theory
AU - Gould, Tim
AU - Pittalis, Stefano
AU - Toulouse, Julien
AU - Kraisler, Eli
AU - Kronik, Leeor
N1 - Publisher Copyright:
© 2019 the Owner Societies.
PY - 2019
Y1 - 2019
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85072367030&partnerID=8YFLogxK
U2 - 10.1039/c9cp03633d
DO - 10.1039/c9cp03633d
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
C2 - 31490521
AN - SCOPUS:85072367030
SN - 1463-9076
VL - 21
SP - 19805
EP - 19815
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 36
ER -