Predicting Accurate Electronic Excitation Transfer Rates via Marcus Theory with Boys or Edmiston-Ruedenberg Localized Diabatization

摘要

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