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Incorporation of the Fermi–Amaldi Term into Direct Energy Kohn–Sham Calculations

Dillon, Daisy J.; Tozer, David J.

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Authors

Daisy J. Dillon



Abstract

In direct energy Kohn–Sham (DEKS) theory, the density functional theory electronic energy equals the sum of occupied orbital energies, obtained from Kohn–Sham-like orbital equations involving a shifted Hartree exchange–correlation potential, which must be approximated. In the present study, the Fermi–Amaldi term is incorporated into approximate DEKS calculations, introducing the required −1/r contribution to the exchange–correlation component of the shifted potential in asymptotic regions. It also provides a mechanism for eliminating one-electron self-interaction error, and it introduces a nonzero exchange–correlation component of the shift in the potential that is of appropriate magnitude. The resulting electronic energies are very sensitive to the methodologies considered, whereas the highest occupied molecular orbital energies and exchange–correlation potentials are much less sensitive and are similar to those obtained from DEKS calculations using a conventional exchange–correlation functional.

Journal Article Type Article
Acceptance Date Dec 15, 2021
Online Publication Date Jan 3, 2022
Publication Date Feb 8, 2022
Deposit Date Jan 5, 2022
Publicly Available Date Jan 3, 2023
Journal Journal of Chemical Theory and Computation
Print ISSN 1549-9618
Electronic ISSN 1549-9626
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 18
Issue 2
Pages 703-709
DOI https://doi.org/10.1021/acs.jctc.1c00840
Public URL https://durham-repository.worktribe.com/output/1219488

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.1c00840






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