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Bridge-mediated electron transfer (ET) between a donor and an acceptor isprototypical for the description of numerous most important ET scenarios. Whilemulti-step ET and the interplay of sequential and direct superexchange transferpathways in the donor-bridge-acceptor (D-B-A) model is increasingly understood,the influence off-diagonal system-bath interactions on the transfer dynamics isless explored. Off-diagonal interactions account for the dependence of the ETcoupling elements on nuclear coordinates (non-Condon effects) and are typicallyneglected. Here we numerically investigate with quasi-adiabatic propagator pathintegral (QUAPI) simulations the impact of off-diagonal system-environmentinteractions on the transfer dynamics for a wide range of scenarios in theD-B-A model. We demonstrate that off-diagonal system-environment interactionscan have profound impact on the bridge-mediated ET dynamics. In the consideredscenarios the dynamics itself does not allow for a rigorous assignment of theunderlying transfer mechanism. Further, we demonstrate how off-diagonalsystem-environment interaction mediates anomalous localization by preventinglong-time depopulation of the bridge B and how coherent transfer dynamicsbetween donor D and acceptor A can be facilitated. The arising non-exponentialshort-time dynamics and coherent oscillations are interpreted within anequivalent Hamiltonian representation of a primary reaction coordinate modelthat reveals how the complex vibronic interplay of vibrational and electronicdegrees of freedom underlying the non-Condon effects can imposedonor-to-acceptor coherence transfer on short timescales.

On the Role of Non-Diagonal System-Environment Interactions in Bridge-Mediated Electron Transfer