Condensed phase electron transfer beyond the Condon approximation

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...

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Bibliographic Details
Main Authors: Mavros, Michael G. (Author), Hait, Diptarka (Contributor), Van Voorhis, Troy (Contributor), Mavros, Michael George (Contributor)
Format: Article
Language:English
Published: American Chemical Society (ACS), 2018-04-30T18:09:08Z.
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Summary: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.
National Science Foundation (U.S.) (Grant CHE-1464804)