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Issue 23, 2007
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A well-tempered density functional theory of electrons in molecules

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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 a−10 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.

Graphical abstract: A well-tempered density functional theory of electrons in molecules

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Article information

08 Dec 2006
02 Feb 2007
First published
01 Mar 2007

Phys. Chem. Chem. Phys., 2007,9, 2932-2941
Article type
Invited Article

A well-tempered density functional theory of electrons in molecules

E. Livshits and R. Baer, Phys. Chem. Chem. Phys., 2007, 9, 2932
DOI: 10.1039/B617919C

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