Skip to main content

Research Repository

Advanced Search

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

Wiggins, P; Williams, JAG; Tozer, DJ

Excited state surfaces in density functional theory: A new twist on an old problem Thumbnail


Authors

P Wiggins

JAG Williams



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.

Citation

Wiggins, P., Williams, J., & Tozer, D. (2009). Excited state surfaces in density functional theory: A new twist on an old problem. The Journal of Chemical Physics, 131(9), Article 091101. https://doi.org/10.1063/1.3222641

Journal Article Type Article
Publication Date Sep 1, 2009
Deposit Date Feb 6, 2012
Publicly Available Date Oct 29, 2012
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 131
Issue 9
Article Number 091101
DOI https://doi.org/10.1063/1.3222641
Keywords Charge transfer states, Density functional theory, Excited states, Ground states, Molecular configurations, Organic compounds.

Files

Published Journal Article (381 Kb)
PDF

Copyright 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





You might also like



Downloadable Citations