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Scientific article
English

Gradient-corrected exchange potential with the correct asymptotic behavior and the corresponding exchange-energy functional obtained from the virial theorem

Contributors

Lembarki, A.; Rogemond, François; Chermette, Henry

Published in

Physical review. A, General physics, vol. 52, no. 5, p. 3704-3710

Publication date

1995

Abstract

In density-functional theory (DFT), Perdew, Parr, Levy, and Balduz [Phys. Rev. Lett. 49, 1691 (1982)] have shown that for all the electronic systems, the energy of the highest occupied molecular orbital (HOMO) is equal to the negative of the ionization potential. This equality is not recovered within the different approximations of the exchange-correlation functional proposed in the literature. The main reason is that the exchange-correlation potentials of various functionals used in DFT calculations decay rapidly to zero whereas they should exhibit a Coulombic asymptotic -1/r behavior. In this work we propose a gradient-corrected (GC) exchange potential with a correct asymptotic -1/r form for large values of r. The energy of the HOMO calculated with this potential is improved compared to the local-density approximation (LDA) and to the GC functionals widely used in the DFT. Our HOMO eigenvalues are compared to the optimized-potential-model eigenvalues which are the exact values for the exchange-only potential. Using the fact that the LDA satisfies the virial theorem, the exchange energy corresponding to this GC exchange potential can be calculated under a simple assumption.

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

LEMBARKI, A., ROGEMOND, François, CHERMETTE, Henry. Gradient-corrected exchange potential with the correct asymptotic behavior and the corresponding exchange-energy functional obtained from the virial theorem. In: Physical review. A, General physics, 1995, vol. 52, n° 5, p. 3704–3710. doi: 10.1103/PhysRevA.52.3704

Main files (1)

Article (Published version)

Identifiers

Additional URL for this publication

http://prola.aps.org/pdf/PRA/v52/i5/p3704_1

Journal ISSN

0556-2791
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Technical informations

Creation

21/09/2009 16:03:57

First validation

21/09/2009 16:03:57

Update

14/03/2023 15:12:11

Status update

14/03/2023 15:12:11

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