Relationship between long-range charge-transfer excitation energy error and integer discontinuity in Kohn-Sham theory

Tozer, D.J.

doi:10.1063/1.1633756

Relationship between long-range charge-transfer excitation energy error and integer discontinuity in Kohn-Sham theory

Tozer, D.J.

Authors

Professor David Tozer d.j.tozer@durham.ac.uk
Professor

Abstract

Charge-transfer (CT) electronic excitation energies are known to be very poorly predicted by time-dependent density functional theory (TDDFT) using local exchange-correlation functionals. Insight into this observation is provided by a simple analysis of intermolecular CT excitations at infinite separation. It is argued that the first TDDFT CT excitation energy approximately underestimates the experimental excitation by the average of the integer discontinuities of the donor and acceptor molecules; errors are of the order of several electron volts.

Citation

Tozer, D. (2003). Relationship between long-range charge-transfer excitation energy error and integer discontinuity in Kohn-Sham theory. The Journal of Chemical Physics, 119(24), 12697-12699. https://doi.org/10.1063/1.1633756

Journal Article Type	Article
Publication Date	Dec 1, 2003
Deposit Date	May 10, 2007
Publicly Available Date	Apr 26, 2011
Journal	Journal of Chemical Physics
Print ISSN	0021-9606
Electronic ISSN	1089-7690
Publisher	American Institute of Physics
Peer Reviewed	Peer Reviewed
Volume	119
Issue	24
Pages	12697-12699
DOI	https://doi.org/10.1063/1.1633756

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Copyright (2003) American Institute of Physics.
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Tozer, D. J. (2003) 'Relationship between long-range charge-transfer excitation energy error and integer discontinuity in Kohn-Sham theory.', Journal of chemical physics., 119 (24). pp. 12697-12699.

and may be found at http://dx.doi.org/10.1063/1.1633756