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

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 $N$, and inverted to produce accurate KS potentials $v_s^N(r)$. We study the dependence of the KS potential on $N$, and in particular we numerically reproduce the theoretically predicted spatially constant discontinuity of $v_s^N(r)$ as $N$ 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 $N$. This leads us to propose a simple approximation of the KS potential $v_s^N(r)$ at any fractional electron number $N$ which uses only quantities of the systems with the adjacent integer electron numbers.

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Cited by in corpus (3)

• 'Hartree-exchange' in ensemble density functional theory: Avoiding the non-uniqueness disaster
• Exact ensemble density functional theory for excited states in a model system: investigating the weight dependence of the correlation energy
• Kohn-Sham potential for a strongly correlated finite system with fractional occupancy