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Communication: Predictive partial linearized path integral simulation of condensed phase electron transfer dynamics

机译:通信:凝聚相电子传输动力学的预测部分线性化路径积分模拟

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摘要

A partial linearized path integral approach is used to calculate the condensed phase electron transfer (ET) rate by directly evaluating the flux-flux/flux-side quantum time correlation functions. We demonstrate for a simple ET model that this approach can reliably capture the transition between non-adiabatic and adiabatic regimes as the electronic coupling is varied, while other commonly used semi-classical methods are less accurate over the broad range of electronic couplings considered. Further, we show that the approach reliably recovers the Marcus turnover as a function of thermodynamic driving force, giving highly accurate rates over four orders of magnitude from the normal to the inverted regimes. We also demonstrate that the approach yields accurate rate estimates over five orders of magnitude of inverse temperature. Finally, the approach outlined here accurately captures the electronic coherence in the flux-flux correlation function that is responsible for the decreased rate in the inverted regime.
机译:通过直接评估通量-通量/通量侧量子时间相关函数,使用部分线性路径积分方法来计算凝聚相电子传输(ET)速率。我们证明了一个简单的ET模型,该方法可以可靠地捕获随着电子耦合变化而在非绝热和绝热状态之间的过渡,而其他常用的半经典方法在考虑的广泛电子耦合范围内准确性较差。此外,我们证明了该方法能够可靠地恢复作为热力学驱动力函数的马库斯周转率,从而在从正常状态到反向状态的四个数量级上提供高度准确的速率。我们还证明,该方法可在逆温度的五个数量级上产生准确的速率估算。最后,这里概述的方法可以准确地捕获通量-通量相关函数中的电子相干性,这是导致倒置速率降低的原因。

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