Adiabatic vs. nonadiabatic electron transfer and longitudinal solvent dielectric relaxation: Beyond the Debye model
Adiabatic vs. nonadiabatic electron transfer and longitudinal solvent dielectric relaxation: Beyond the Debye model
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DOI：
10.1021/j100299a005
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发表时间：
1987-07
期刊：
影响因子：
--
通讯作者：
M. Sparpaglione;S. Mukamel
中科院分区：
文献类型：
--
作者：
M. Sparpaglione;S. Mukamel
利用刘维尔空间中密度矩阵的展开并利用与非线性光线形状问题的类比，发展了极性介质中电子转移速率的理论。总体和相干性（分别是密度矩阵的对角线和非对角线元素）之间时间尺度的分离使我们能够在非绝热耦合中将速率近似求和到无限阶。导出了速率的封闭表达式和绝热性的新颖标准，其中涉及溶剂 c (k, oj) 的整个频率和波矢量相关介电函数。获得了以c(k,w)表示的相关溶剂时间尺度的正确定义，该定义不限于德拜模型。分析了溶剂纵向介电弛豫在诱导从非绝热状态到绝热状态的交叉中的作用。
A theory for electron-transfer rates in a polar medium is developedusing an expansion of the density matrix in Liouville space and utilizing the analogy with the problem of nonlinear optical line shapes. A separation of time scales between the populations and coherences (diagonal and off-diagonal elements of the density matrix, respectively) allows us to carry an approximate summation of the rate to infinite order in the nonadiabatic coupling. A closed expression for the rate and a novel criterion for adiabaticity, involving the entire frequency and wavevector-dependent dielectric function of the solvent c (k, oj) are derived. A proper definition of the relevant solvent time scale in terms of c (k, w), which is not restricted to the Debye model, is obtained. The role of the solvent longitudinal dielectric relaxation in inducing the crossover from the nonadiabatic to the adiabatic regimes is analyzed.