Approximating the Shifted Hartree-Exchange-Correlation Potential in Direct Energy Kohn–Sham Theory
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 eq...
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Published in | Journal of chemical theory and computation Vol. 14; no. 2; pp. 684 - 692 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
13.02.2018
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Subjects | |
Online Access | Get full text |
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Summary: | 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. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1549-9618 1549-9626 |
DOI: | 10.1021/acs.jctc.7b01060 |