Condensed phase electron transfer beyond the Condon approximation
Author(s)Mavros, Michael G.; Hait, Diptarka; Van Voorhis, Troy; Mavros, Michael George
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Condensed phase electron transfer problems are often simplified by making the Condon approximation: the approximation that the coupling connecting two charge-transfer diabatic states is a constant. Unfortunately, the Condon approximation does not predict the existence of conical intersections, which are ubiquitous in both gas-phase and condensed-phase photochemical dynamics. In this paper, we develop a formalism to treat condensed-phase dynamics beyond the Condon approximation. We show that even for an extremely simple test system, hexaaquairon(ii)/hexaaquairon(iii) self-exchange in water, the electronic coupling is expected to fluctuate rapidly and non-Condon effects must be considered to obtain quantitatively accurate ultrafast nonequilibrium dynamics. As diabatic couplings are expected to fluctuate substantially in many condensed-phase electron transfer systems, non-Condon effects may be essential to quantitatively capture accurate short-time dynamics.
Journal of Chemical Physics
American Chemical Society (ACS)
Mavros, Michael G. et al. “Condensed Phase Electron Transfer Beyond the Condon Approximation.” The Journal of Chemical Physics 145, 21 (December 2016): 214105
Author's final manuscript