Multistate electron transfer dynamics in the condensed phase: exact calculations from the reduced hierarchy equations of motion approach.
Multistate electron transfer dynamics in the condensed phase: exact calculations from the reduced hierarchy equations of motion approach.
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DOI：
10.1063/1.3428674
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发表时间：
2010-06
期刊：
影响因子：
--
通讯作者：
Midori Tanaka;Y. Tanimura
中科院分区：
文献类型：
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作者：
Midori Tanaka;Y. Tanimura
与欧姆热浴耦合的多个位移振荡器用于描述耗散环境中的电子转移（ET）。通过执行规范变换，模型被简化为与具有布朗光谱分布的热浴耦合的多级系统。引入了一种简化的层次运动方程方法，用于对具有各种振荡器配置、不同非绝热耦合强度和阻尼率以及不同温度下的三能级系统的动力学进行严格的数值模拟。降低密度矩阵元素的时间演化说明了电子态和振动态之间相干性的相互作用。 ET 反应速率定义为通量-通量相关函数，使用系统对外部扰动的线性响应作为活化能的函数来计算。由于反应物和产物状态之间存在中间态，结果在小激活状态下表现出不对称的倒抛物线轮廓，而在大激活能量状态下则呈现出缓慢衰减的轮廓，这是由量子相干跃迁引起的。
Multiple displaced oscillators coupled to an Ohmic heat bath are used to describe electron transfer (ET) in a dissipative environment. By performing a canonical transformation, the model is reduced to a multilevel system coupled to a heat bath with the Brownian spectral distribution. A reduced hierarchy equations of motion approach is introduced for numerically rigorous simulation of the dynamics of the three-level system with various oscillator configurations, for different nonadiabatic coupling strengths and damping rates, and at different temperatures. The time evolution of the reduced density matrix elements illustrates the interplay of coherences between the electronic and vibrational states. The ET reaction rates, defined as a flux-flux correlation function, are calculated using the linear response of the system to an external perturbation as a function of activation energy. The results exhibit an asymmetric inverted parabolic profile in a small activation regime due to the presence of the intermediate state between the reactant and product states and a slowly decaying profile in a large activation energy regime, which arises from the quantum coherent transitions.