Dynamic solvent effects on outer‐sphere electron transfer
Dynamic solvent effects on outer‐sphere electron transfer
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DOI：
10.1063/1.453184
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发表时间：
1987-08
影响因子：
4.4
通讯作者：
I. Rips;J. Jortner
中科院分区：
文献类型：
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作者：
I. Rips;J. Jortner
在本文中，我们提出了在极性溶剂中的外层电子转移（ET）的理论研究结果，通过改变仅来自外部介质的响应的电荷分布来修改核状态。该系统的模型哈密顿量对应于两个抛物型非绝热势面之间的绝热耦合。利用真实的-时间路径积分形式推导了高斯近似下介质的影响泛函和ET率的一般表达式。ET率明确评估的特定情况下，其特征在于由德拜介电弛豫函数的介质。我们探索了反应坐标的动力学和ET过程的特征之间的关系，推导了ET速率的表达式，它在非绝热和溶剂控制的绝热极限之间架起了桥梁。我们建立简单的标准的有效性范围内的各种描述的ET…
In this paper we present the results of a theoretical study of outer‐sphere electron transfer (ET) in a polar solvent, with the modification of the nuclear states by the change in the charge distribution originating solely from the response of the exterior medium. The model Hamiltonian for the system corresponds to two parabolic diabatic potential surfaces with adiabatic coupling between them. The real‐time path integral formalism is utilized to derive the general expressions for the influence functional of the medium in the Gaussian approximation and for the ET rate. The ET rate is explicitly evaluated for the particular case of a medium characterized by the Debye dielectric relaxation function. We explore the relation between the dynamics of the reaction coordinate and the character of the ET process, deriving an expression for the ET rate, which bridges between the nonadiabatic and the solvent‐controlled adiabatic limits. We establish simple criteria for the validity range of various descriptions of ET...