Diminished gradient dependence of density functionals

Constraint satisfaction and self-interaction correction

G. Csonka, Oleg A. Vydrov, Gustavo E. Scuseria, Adrienn Ruzsinszky, John P. Perdew

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation for the exchange-correlation energy functional has two nonempirical constructions, based on satisfaction of universal exact constraints on the hole density or on the energy. We show here that, by identifying one possible free parameter in exchange and a second in correlation, we can continue to satisfy these constraints while diminishing the gradient dependence almost to zero (i.e., almost recovering the local spin density approximation or LSDA). This points out the important role played by the Perdew-Wang 1991 nonempirical hole construction in shaping PBE and later constructions. Only the undiminished PBE is good for atoms and molecules, for reasons we present, but a somewhat diminished PBE could be useful for solids; in particular, the surface energies of solids could be improved. Even for atoms and molecules, a strongly diminished PBE works well when combined with a scaled-down self-interaction correction (although perhaps not significantly better than LSDA). This shows that the undiminished gradient dependence of PBE and related functionals works somewhat like a scaled-down self-interaction correction to LSDA.

Original languageEnglish
Article number244107
JournalThe Journal of Chemical Physics
Volume126
Issue number24
DOIs
Publication statusPublished - 2007

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functionals
gradients
Atoms
Molecules
interactions
approximation
Interfacial energy
surface energy
atoms
molecules
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Diminished gradient dependence of density functionals : Constraint satisfaction and self-interaction correction. / Csonka, G.; Vydrov, Oleg A.; Scuseria, Gustavo E.; Ruzsinszky, Adrienn; Perdew, John P.

In: The Journal of Chemical Physics, Vol. 126, No. 24, 244107, 2007.

Research output: Contribution to journalArticle

Csonka, G. ; Vydrov, Oleg A. ; Scuseria, Gustavo E. ; Ruzsinszky, Adrienn ; Perdew, John P. / Diminished gradient dependence of density functionals : Constraint satisfaction and self-interaction correction. In: The Journal of Chemical Physics. 2007 ; Vol. 126, No. 24.
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