Predicting accurate electronic excitation transfer rates via Marcus theory with boys or edmiston-ruedenberg localized diabatization

Joseph E. Subotnik, Josh Vura-Weis, Alex J. Sodt, Mark A. Ratner

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We model the triplet - triplet energy-transfer experiments from the Closs group [Closs, G. L.; et al. J. Am. Chem. Soc. 1988, 110, 2652.] using a combination of Marcus theory and either Boys or Edmiston - Ruedenberg localized diabatization, and we show that relative and absolute rates of electronic excitation transfer may be computed successfully. For the case where both the donor and acceptor occupy equatorial positions on a rigid cyclohexane bridge, we find βcalc = 2.8 per C-C bond, compared with the experimental value βexp = 2.6. This work highlights the power of using localized diabatization methods as a tool for modeling nonequilibrium processes.

Original languageEnglish
Pages (from-to)8665-8675
Number of pages11
JournalJournal of Physical Chemistry A
Issue number33
Publication statusPublished - Aug 26 2010


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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