Rationale for mixing exact exchange with density functional approximations

John P. Perdew; Matthias Ernzerhof; Kieron Burke

doi:10.1063/1.472933

journal article Dec 08, 1996

Rationale for mixing exact exchange with density functional approximations

John P. Perdew Matthias Ernzerhof Kieron Burke

The Journal of Chemical Physics Vol. 105 No. 22 pp. 9982-9985 · AIP Publishing

View at Publisher Save 10.1063/1.472933

Abstract

Density functional approximations for the exchange-correlation energy EDFAxc of an electronic system are often improved by admixing some exact exchange Ex: Exc≊EDFAxc+(1/n)(Ex−EDFAx). This procedure is justified when the error in EDFAxc arises from the λ=0 or exchange end of the coupling-constant integral ∫10 dλ EDFAxc,λ. We argue that the optimum integer n is approximately the lowest order of Görling–Levy perturbation theory which provides a realistic description of the coupling-constant dependence Exc,λ in the range 0≤λ≤1, whence n≊4 for atomization energies of typical molecules. We also propose a continuous generalization of n as an index of correlation strength, and a possible mixing of second-order perturbation theory with the generalized gradient approximation.

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Details

Published: Dec 08, 1996
Vol/Issue: 105(22)
Pages: 9982-9985

Authors

J

John P. Perdew

Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118

M

Matthias Ernzerhof

Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118

K

Kieron Burke

Department of Chemistry, Rutgers University, Camden, New Jersey 08102

Cite This Article

John P. Perdew, Matthias Ernzerhof, Kieron Burke (1996). Rationale for mixing exact exchange with density functional approximations. The Journal of Chemical Physics, 105(22), 9982-9985. https://doi.org/10.1063/1.472933

Rationale for mixing exact exchange with density functional approximations

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