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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer: Comparison of Explicit and Implicit Solvent Simulations
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Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer: Comparison of Explicit and Implicit Solvent Simulations

机译：光诱导质子耦合电子转移的非绝热动力学：显式和隐式溶剂模拟的比较

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摘要

Theoretical approaches for simulating the ultrafast dynamics of photoinduced proton-coupled electron transfer (PCET) reactions in solution are developed and applied to a series of model systems. These processes are simulated by propagating nonadiabatic surface hopping trajectories on electron-proton vibronic surfaces that depend on the solute and solvent nuclear coordinates. The PCET system is represented by a four-state empirical valence bond model, and the solvent is treated either as explicit solvent molecules or as a dielectric continuum, in which case the solvent dynamics is described in terms of two collective solvent coordinates corresponding to the energy gaps associated with electron and proton transfer. The explicit solvent simulations reveal two distinct solvent relaxation time scales, where the faster time scale relaxation corresponds to librational motions of solvent molecules in the first solvation shell, and the slower time scale relaxation corresponds to the bulk solvent dielectric response. The charge transfer dynamics is strongly coupled to both the fast and slow time scale solvent dynamics. The dynamical multistate continuum theory is extended to include the effects of two solvent relaxation time scales, and the resulting coupled generalized Langevin equations depend on parameters that can be extracted from equilibrium molecular dynamics simulations. The implicit and explicit solvent approaches lead to qualitatively similar charge transfer and solvent dynamics for model PCET systems, suggesting that the implicit solvent treatment captures the essential elements of the nonequilibrium solvent dynamics for many systems. A combination of implicit and explicit solvent approaches vill enable the investigation of photoinduced PCET processes in a variety of condensed phase systems.
机译：开发了用于模拟溶液中光致质子耦合电子转移（PCET）反应的超快动力学的理论方法，并将其应用于一系列模型系统。通过在取决于质子和溶剂核坐标的电子-质子振动子表面上传播非绝热表面跳跃轨迹来模拟这些过程。 PCET系统由四态经验价键模型表示，并且溶剂被视为显式溶剂分子或介电连续体，在这种情况下，溶剂动力学用对应于能量的两个集体溶剂坐标来描述与电子和质子转移相关的间隙。显式的溶剂模拟显示了两个不同的溶剂弛豫时间尺度，其中较快的时间尺度弛豫对应于第一溶剂化壳中溶剂分子的自由运动，而较慢的时间尺度弛豫对应于整体溶剂介电响应。电荷转移动力学与快速和慢速时间尺度的溶剂动力学密切相关。扩展了动态多态连续体理论，以包括两个溶剂弛豫时间尺度的影响，并且由此产生的耦合的广义Langevin方程取决于可从平衡分子动力学模拟中提取的参数。对于模型PCET系统，隐式和显式溶剂方法可导致定性相似的电荷转移和溶剂动力学，表明隐式溶剂处理捕获了许多系统非平衡溶剂动力学的基本要素。隐式和显式溶剂方法的结合将使人们能够研究各种冷凝相系统中的光诱导PCET过程。

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