Phys. Rev. A 104, 032803 (2021) - Exact expressions for the height of the interatomic step in the exchange-correlation potential from the derivative discontinuity of the energy

Exact expressions for the height of the interatomic step in the exchange-correlation potential from the derivative discontinuity of the energy

M. J. P. Hodgson

Phys. Rev. A 104, 032803 – Published 2 September 2021

Abstract

Popular approximations to the exchange-correlation (xc) energy of density-functional theory do not yield the spatial “step” structures in the exact xc potential which are necessary to describe dissociation and electron excitation with the Kohn-Sham (KS) system. Via the discontinuity in the derivative of the xc energy as a function of electron number I derive exact analytic expressions in terms of the KS single-particle energies for the height of the step in the xc potential between a variety of open- and closed-shell atoms within stretched molecules.

Received 9 April 2021
Revised 18 August 2021
Accepted 19 August 2021

DOI:https://doi.org/10.1103/PhysRevA.104.032803

©2021 American Physical Society

Physics Subject Headings (PhySH)

Atomic & molecular structure Chemical binding Chemical bonding Electronic excitation & ionization Electronic structure of atoms & molecules

Electron affinity

Density functional theory Density functional theory development Exact solutions for many-body systems First-principles calculations Quantum chemistry methods Quantum correlations, foundations & formalism Schroedinger equation

Condensed Matter, Materials & Applied PhysicsAtomic, Molecular & Optical

Authors & Affiliations

M. J. P. Hodgson ^*

Department of Physics, Durham University, South Road, Durham DH1 3LE, United Kingdom and The European Theoretical Spectroscopy Facility

^*matthew.j.hodgson@durham.ac.uk; http://www-users.york.ac.uk/~mjph501/

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Issue

Vol. 104, Iss. 3 — September 2021

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