English

Kohn-Sham potentials in exact density-functional theory at non-integer electron numbers

Chemical Physics 2014-11-14 v2 Computational Physics

Abstract

Within exact electron density-functional theory, we investigate Kohn-Sham (KS) potentials, orbital energies, and non-interacting kinetic energies of the fractional ions of Li, C and F. We use quantum Monte Carlo densities as input, which are then fitted, interpolated at non-integer electron numbers NN, and inverted to produce accurate KS potentials vsN(r)v_s^N(r). We study the dependence of the KS potential on NN, and in particular we numerically reproduce the theoretically predicted spatially constant discontinuity of vsN(r)v_s^N(r) as NN passes through an integer. We further show that, for all the cases considered, the inner orbital energies and the non-interacting kinetic energy are nearly piecewise linear functions of NN. This leads us to propose a simple approximation of the KS potential vsN(r)v_s^N(r) at any fractional electron number NN which uses only quantities of the systems with the adjacent integer electron numbers.

Keywords

Cite

@article{arxiv.1407.2707,
  title  = {Kohn-Sham potentials in exact density-functional theory at non-integer electron numbers},
  author = {Tim Gould and Julien Toulouse},
  journal= {arXiv preprint arXiv:1407.2707},
  year   = {2014}
}
R2 v1 2026-06-22T05:00:19.115Z