Issue 36, 2019

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

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.

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

Article information

Article type
Paper
Submitted
27 জুন 2019
Accepted
23 আগ. 2019
First published
28 আগ. 2019

Phys. Chem. Chem. Phys., 2019,21, 19805-19815

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

T. Gould, S. Pittalis, J. Toulouse, E. Kraisler and L. Kronik, Phys. Chem. Chem. Phys., 2019, 21, 19805 DOI: 10.1039/C9CP03633D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements