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首页> 外文期刊>The Journal of Chemical Physics >Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods
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Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods

机译：使用环聚合物分子动力学直接模拟电子转移：与半经典瞬子理论和精确量子方法的比较

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摘要

The use of ring polymer molecular dynamics (RPMD) for the direct simulation of electron transfer (ET) reaction dynamics is analyzed in the context of Marcus theory, semiclassical instanton theory, and exact quantum dynamics approaches. For both fully atomistic and system-bath representations of condensed-phase ET, we demonstrate that RPMD accurately predicts both ET reaction rates and mechanisms throughout the normal and activationless regimes of the thermodynamic driving force. Analysis of the ensemble of reactive RPMD trajectories reveals the solvent reorganization mechanism for ET that is anticipated in the Marcus rate theory, and the accuracy of the RPMD rate calculation is understood in terms of its exact description of statistical fluctuations and its formal connection to semiclassical instanton theory for deep-tunneling processes. In the inverted regime of the thermodynamic driving force, neither RPMD nor a related formulation of semiclassical instanton theory capture the characteristic turnover in the reaction rate; comparison with exact quantum dynamics simulations reveals that these methods provide inadequate quantization of the real-time electronic-state dynamics in the inverted regime.
机译：在Marcus理论，半经典瞬子理论和精确的量子动力学方法的背景下，分析了使用环状聚合物分子动力学（RPMD）直接模拟电子转移（ET）反应动力学。对于冷凝相ET的完全原子表示和系统浴表示，我们证明RPMD可以准确预测整个热力学驱动力的正常和无激活状态下ET的反应速率和机理。通过对反应性RPMD轨迹的整体分析，揭示了马库斯速率理论中预期的ET溶剂重组机制，并且根据其对统计波动的精确描述以及与半经典瞬时子的形式联系，可以理解RPMD速率计算的准确性。隧道过程理论。在热力学驱动力的倒置状态下，RPMD或半经典瞬子理论的相关表述均未捕获反应速率中的特征转换。与精确的量子动力学模拟的比较表明，这些方法在倒置状态下对实时电子态动力学的量化不足。

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