On the role of non-diagonal system-environment interactions in bridge-mediated electron transfer.
On the role of non-diagonal system-environment interactions in bridge-mediated electron transfer.
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DOI：
10.1063/5.0027976
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发表时间：
2020-11
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影响因子：
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通讯作者：
Nirmalendu Acharyya;R. Ovcharenko;B. Fingerhut
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作者：
Nirmalendu Acharyya;R. Ovcharenko;B. Fingerhut
供体和受体之间的桥介导的电子转移（ET）是描述许多最重要的ET场景的原型。虽然多步ET和顺序和直接的超交换转移途径的相互作用在供体-桥-受体（D-B-A）模型越来越多地了解，非对角系统浴相互作用的转移动力学的影响较少探索。非对角相互作用解释了ET耦合元素对核坐标的依赖性（非康登效应），并且通常被忽略。在这里，我们用准绝热传播子路径积分模拟数值研究了非对角系统-环境相互作用对D-B-A模型中各种场景的传输动力学的影响。我们证明了非对角系统-环境相互作用可以对桥介导的ET动力学产生深远的影响。在所考虑的情况下，动态本身不允许一个严格的基本转让机制的分配。此外，我们证明了如何非对角系统环境相互作用介导的异常本地化，防止长时间的人口减少的桥梁B和如何相干转移动态之间的供体D和受体A可以促进。所产生的非指数短时间动力学和相干振荡内解释一个等效的哈密顿表示的初级反应坐标模型，揭示了如何复杂的振动和电子的相互作用的振动和非康登效应的自由度可以施加捐助者到受体的相干转移短的时间尺度。
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.