Condensed phase electron transfer beyond the Condon approximation.

Abstract

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.

DOI: 10.1063/1.4971166

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Cite this paper

@article{Mavros2016CondensedPE, title={Condensed phase electron transfer beyond the Condon approximation.}, author={Michael G Mavros and Diptarka Hait and Troy van Voorhis}, journal={The Journal of chemical physics}, year={2016}, volume={145 21}, pages={214105} }