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J Chem Phys. 2007 Jun 28;126(24):244107.

Diminished gradient dependence of density functionals: constraint satisfaction and self-interaction correction.

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1
Department of Chemistry, Budapest University of Technology and Economics, H-1521 Budapest, Hungary.

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.

PMID:
17614537
DOI:
10.1063/1.2743985
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