Approximating the Shifted Hartree-Exchange-Correlation Potential in Direct Energy Kohn–Sham Theory

Sharpe, Daniel J.; Levy, Mel; Tozer, David J.

doi:10.1021/acs.jctc.7b01060

Approximating the Shifted Hartree-Exchange-Correlation Potential in Direct Energy Kohn–Sham Theory

Sharpe, Daniel J.; Levy, Mel; Tozer, David J.

Authors

Daniel J. Sharpe

Mel Levy

Professor David Tozer d.j.tozer@durham.ac.uk
Professor

Abstract

Levy and Zahariev [Phys. Rev. Lett. 113 113002 (2014)] have proposed a new approach for performing density functional theory calculations, termed direct energy Kohn–Sham (DEKS) theory. In this approach, the electronic energy equals the sum of orbital energies, obtained from Kohn–Sham-like orbital equations involving a shifted Hartree-exchange-correlation potential, which must be approximated. In the present study, density scaling homogeneity considerations are used to facilitate DEKS calculations on a series of atoms and molecules, leading to three nonlocal approximations to the shifted potential. The first two rely on preliminary Kohn–Sham calculations using a standard generalized gradient approximation (GGA) exchange-correlation functional and the results illustrate the benefit of describing the dominant Hartree component of the shift exactly. A uniform electron gas analysis is used to eliminate the need for these preliminary Kohn–Sham calculations, leading to a potential with an unconventional form that yields encouraging results, providing strong motivation for further research in DEKS theory.

Citation

Sharpe, D. J., Levy, M., & Tozer, D. J. (2018). Approximating the Shifted Hartree-Exchange-Correlation Potential in Direct Energy Kohn–Sham Theory. Journal of Chemical Theory and Computation, 14(2), 684-692. https://doi.org/10.1021/acs.jctc.7b01060

Journal Article Type	Article
Acceptance Date	Jan 3, 2018
Online Publication Date	Jan 3, 2018
Publication Date	Mar 1, 2018
Deposit Date	Jan 24, 2018
Publicly Available Date	Jan 3, 2019
Journal	Journal of Chemical Theory and Computation
Print ISSN	1549-9618
Electronic ISSN	1549-9626
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	14
Issue	2
Pages	684-692
DOI	https://doi.org/10.1021/acs.jctc.7b01060

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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.7b01060.