A well-tempered density functional theory of electrons in molecules

Ester Livshits, Roi Baer*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

350 Scopus citations

Abstract

This Invited Article reports extensions of a recently developed approach to density functional theory with correct long-range behavior (R. Baer and D. Neuhauser, Phys. Rev. Lett., 2005, 94, 043002). The central quantities are a splitting functional γ[n] and a complementary exchange-correlation functional EγXC[n]. We give a practical method for determining the value of γ in molecules, assuming an approximation for EγXC is given. The resulting theory shows good ability to reproduce the ionization potentials for various molecules. However it is not of sufficient accuracy for forming a satisfactory framework for studying molecular properties. A somewhat different approach is then adopted, which depends on a density-independent γ and an additional parameter w eliminating part of the local exchange functional. The values of these two parameters are obtained by best-fitting to experimental atomization energies and bond lengths of the molecules in the G2(1) database. The optimized values are γ = 0.5 a0-1 and w = 0.1. We then examine the performance of this slightly semi-empirical functional for a variety of molecular properties, comparing to related works and experiment. We show that this approach can be used for describing in a satisfactory manner a broad range of molecular properties, be they static or dynamic. Most satisfactory is the ability to describe valence, Rydberg and inter-molecular charge-transfer excitations.

Original languageAmerican English
Pages (from-to)2932-2941
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume9
Issue number23
DOIs
StatePublished - 2007

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