Excitation energies and Stokes shifts from a restricted open-shell Kohn-Sham approach
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Van Voorhis_Excitation energies.pdf
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Author(s)
Kowalczyk, Timothy Daniel
Tsuchimochi, Takashi
Chen, Po-Ta
Top, Laken
Van Voorhis, Troy
Date Issued
April 2013
Journal
Journal of Chemical Physics
Publisher
American Institute of Physics
Citation
Kowalczyk, Tim, Takashi Tsuchimochi, Po-Ta Chen, Laken Top, and Troy Van Voorhis. “Excitation energies and Stokes shifts from a restricted open-shell Kohn-Sham approach.” The Journal of Chemical Physics 138, no. 16 (2013): 164101. © 2013 AIP Publishing LLC.
Version
Final published version
Abstract
Restricted open-shell Kohn-Sham (ROKS) theory provides a powerful computational tool for calculating singlet excited state energies and dynamics. However, the possibility of multiple solutions to the ROKS equations — with the associated difficulty of automatically selecting the physically meaningful solution — limits its usefulness for intensive applications such as long-time Born-Oppenheimer molecular dynamics. We present an implementation of ROKS for excited states which prescribes the physically correct solution from an overlap criterion and guarantees that this solution is stationary, allowing for straightforward evaluation of nuclear gradients. The method is used to benchmark ROKS for vertical excitation energies of small and large organic dyes and for the calculation of Stokes shifts. With common density functional approximations, ROKS vertical excitation energies, and Stokes shifts show similar accuracy to those from time-dependent density functional theory and Δ-self-consistent-field approaches. Advantages of the ROKS approach for excited state structure and molecular dynamics are discussed.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
MIT Energy Initiative
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1063/1.4801790
