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Excited state surfaces in density functional theory : a new twist on an old problem.

Wiggins, P. and Williams, J.A.G. and Tozer, D.J. (2009) 'Excited state surfaces in density functional theory : a new twist on an old problem.', Journal of chemical physics., 131 (9). 091101.

Abstract

Excited state surfaces in density functional theory and the problem of charge transfer are considered from an orbital overlap perspective. For common density functional approximations, the accuracy of the surface will not be uniform if the spatial overlap between the occupied and virtual orbitals involved in the excitation has a strong conformational dependence; the excited state surface will collapse toward the ground state in regions where the overlap is very low. This characteristic is used to predict and to provide insight into the breakdown of excited state surfaces in the classic push-pull 4-(dimethylamino)benzonitrile molecule, as a function of twist angle. The breakdown is eliminated using a Coulomb-attenuated functional. Analogous situations will arise in many molecules.

Item Type:Article
Keywords:Charge transfer states, Density functional theory, Excited states, Ground states, Molecular configurations, Organic compounds.
Full text:PDF - Published Version (372Kb)
Status:Peer-reviewed
Publisher Web site:http://dx.doi.org/10.1063/1.3222641
Publisher statement:Copyright (2009) American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Wiggins, P. and Williams, J.A.G. and Tozer, D.J. (2009) 'Excited state surfaces in density functional theory : a new twist on an old problem.', Journal of chemical physics., 131 (9). 091101 and may be found at http://dx.doi.org/10.1063/1.3222641
Record Created:24 Oct 2012 15:50
Last Modified:29 Oct 2012 10:46

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