| Autor: |
Acharyya, Nirmalendu, Ovcharenko, Roman, Fingerhut, Benjamin P. |
| Předmět: |
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| Zdroj: |
Journal of Chemical Physics; 11/14/2020, Vol. 153 Issue 18, p1-12, 12p |
| Abstrakt: |
Bridge-mediated electron transfer (ET) between a donor and an acceptor is prototypical for the description of numerous most important ET scenarios. While multi-step ET and the interplay of sequential and direct superexchange transfer pathways in the donor–bridge–acceptor (D–B–A) model are increasingly understood, the influence of off-diagonal system–bath interactions on the transfer dynamics is less explored. Off-diagonal interactions account for the dependence of the ET coupling elements on nuclear coordinates (non-Condon effects) and are typically neglected. Here, we numerically investigate with quasi-adiabatic propagator path integral simulations the impact of off-diagonal system–environment interactions on the transfer dynamics for a wide range of scenarios in the D–B–A model. We demonstrate that off-diagonal system–environment interactions can have profound impact on the bridge-mediated ET dynamics. In the considered scenarios, the dynamics itself does not allow for a rigorous assignment of the underlying transfer mechanism. Furthermore, we demonstrate how off-diagonal system–environment interaction mediates anomalous localization by preventing long-time depopulation of the bridge B and how coherent transfer dynamics between donor D and acceptor A can be facilitated. The arising non-exponential short-time dynamics and coherent oscillations are interpreted within an equivalent Hamiltonian representation of a primary reaction coordinate model that reveals how the complex vibronic interplay of vibrational and electronic degrees of freedom underlying the non-Condon effects can impose donor-to-acceptor coherence transfer on short timescales. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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