Calculating excited state properties using Kohn-Sham density functional theory

Hanson-Heine, Magnus W.D.; George, Michael W.; Besley, Nicholas A.

Abstract

The accuracy of excited states calculated with Kohn-Sham density functional theory using the maximum overlap method has been assessed for the calculation of adiabatic excitation energies, excited state structures, and excited state harmonic and anharmonic vibrational frequencies for open-shell singlet excited states. The computed Kohn-Sham adiabatic excitation energies are improved significantly by post self-consistent-field spin-purification, but remain too low compared with experiment with a larger error than time-dependent density functional theory. Excited state structures and vibrational frequencies are also improved by spin-purification. The structures show a comparable accuracy to time-dependent density functional theory, while the harmonic vibrational frequencies are found to be more accurate for the majority of vibrational modes. The computed harmonic vibrational frequencies are also further improved by perturbative anharmonic corrections, suggesting a good description of the potential energy surface. Overall, excited state Kohn-Sham density functional theory is shown to provide an efficient method for the calculation of excited state structures and vibrational frequencies in open-shell singlet systems, and provides a promising technique that can be applied to study large systems.

Citation

Hanson-Heine, M. W., George, M. W., & Besley, N. A. (2013). Calculating excited state properties using Kohn-Sham density functional theory. Journal of Chemical Physics, 138(6), Article 064101. https://doi.org/10.1063/1.4789813

• Journal Article Type: Article
• Publication Date: Feb 14, 2013
• Deposit Date: Sep 14, 2015
• Publicly Available Date: Sep 14, 2015
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 138
• Issue: 6
• Article Number: 064101
• DOI: https://doi.org/10.1063/1.4789813
• Keywords: density functional theory
• Public URL: https://nottingham-repository.worktribe.com/output/713390
• Publisher URL: http://scitation.aip.org/content/aip/journal/jcp/138/6/10.1063/1.4789813
• Additional Information: Copyright 2013 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 The journal of chemical physics, v. 138 (064101) and may be found at http://scitation.aip.org/content/aip/journal/jcp/138/6/10.1063/1.4789813