Photoinduced charge transfer (CT) in the condensed phase is an essential component in solar energy conversion, but it is challenging to simulate such a process on the all-atom level. The traditional Marcus theory has been utilized for obtaining CT rate constants between pairs of electronic states but cannot account for the nonequilibrium effects due to the initial nuclear preparation. The recently proposed instantaneous Marcus theory (IMT) and its nonlinear-response formulation allow for incorporating the nonequilibrium nuclear relaxation to electronic transition between two states after the photoexcitation from the equilibrium ground state and provide the time-dependent rate coefficient. In this work, we extend the nonlinear-response IMT method for treating photoinduced CT among general multiple electronic states and demonstrate it in the organic photovoltaic carotenoid–porphyrin–fullerene triad dissolved in explicit tetrahydrofuran solvent. All-atom molecular dynamics simulations were employed to obtain the time correlation functions of energy gaps, which were used to generate the IMT-required time-dependent averages and variances of the relevant energy gaps. Our calculations show that the multistate IMT could capture the significant nonequilibrium effects due to the initial nuclear state preparation, and this is corroborated by the substantial differences between the population dynamics predicted by the multistate IMT and the Marcus theory, where the Marcus theory underestimates the population transfer. The population dynamics by multistate IMT is also shown to have a better agreement with the all-atom nonadiabatic mapping dynamics than the Marcus theory does. Because the multistate nonlinear-response IMT is straightforward and cost-effective in implementation and accounts for the nonequilibrium nuclear effects, we believe this method offers a practical strategy for studying charge transfer dynamics in complex condensed-phase systems.

中文翻译：

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通过多态非线性响应瞬时 Marcus 理论研究凝聚相中的全原子光生电荷转移动力学

凝聚相中的光致电荷转移（CT）是太阳能转换的重要组成部分，但在全原子水平上模拟这一过程具有挑战性。传统的马库斯理论已被用来获得电子态对之间的 CT 速率常数，但无法解释由于初始核准备而产生的非平衡效应。最近提出的瞬时马库斯理论（IMT）及其非线性响应公式允许将非平衡核弛豫纳入平衡基态光激发后两个状态之间的电子跃迁，并提供时间相关的速率系数。在这项工作中，我们扩展了处理一般多电子态光致CT的非线性响应IMT方法，并在溶解于显式四氢呋喃溶剂中的有机光伏类胡萝卜素-卟啉-富勒烯三元组中进行了演示。采用全原子分子动力学模拟获得能隙的时间相关函数，用于生成 IMT 所需的相关能隙的时间相关平均值和方差。我们的计算表明，多态 IMT 可以捕获由于初始核态准备而产生的显着的非平衡效应，并且多态 IMT 预测的种群动态与 Marcus 理论之间的巨大差异证实了这一点，其中 Marcus 理论低估了种群转移。与马库斯理论相比，多态 IMT 的群体动力学也被证明与全原子非绝热映射动力学具有更好的一致性。由于多态非线性响应 IMT 在实施中简单且具有成本效益，并且考虑了非平衡核效应，因此我们相信该方法为研究复杂凝聚相系统中的电荷转移动力学提供了一种实用的策略。