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

Tozer, D.J.

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
• Public URL: https://durham-repository.worktribe.com/output/1568630