Solvent structure and hydrodynamic effects in photoinduced electron transfer
Solvent structure and hydrodynamic effects in photoinduced electron transfer
复制标题
DOI：
10.1063/1.471119
复制
发表时间：
1996-02
影响因子：
4.4
通讯作者：
S. F. Swallen;K. Weidemaier;M. Fayer
中科院分区：
文献类型：
--
作者：
S. F. Swallen;K. Weidemaier;M. Fayer
一种先前发展的描述光诱导电子转移和液体溶液中双相复合的统计力学理论已经被修改，以解释现实的有限体积溶剂效应。本工作介绍了由溶剂引起的重要物理效应，它从根本上影响电荷转移事件的速率和空间分布。溶剂分子的有限体积导致电子供体周围的粒子分布不均匀，这通过双粒子径向分布函数（rdf）纳入理论。rdf的percus_yevick解可以给出溶剂结构g(R)的数值，尽管任何形式的g(R)都可以与该方法一起使用。粒子分布的不均匀性显著影响电子转移速率和正向电子转移形成的离子对的分布，特别是在短时间内。此外，有限的溶剂尺寸会影响任意…
A previously developed statistical mechanical theory describing photo‐induced electron transfer and geminate recombination in liquid solutions has been modified to account for realistic finite‐volume solvent effects. This work introduces physically important effects caused by the solvent which fundamentally affect the rates and spatial distribution of charge transfer events. The finite volume of solvent molecules gives rise to a nonuniform distribution of particles around an electron donor, which is incorporated into the theory by a two‐particle radial distribution function (rdf). The Percus–Yevick solutions for the rdf can give numerically useful values for the solvent structure, g(R) although any form of g(R) can be used with the method. The nonuniform particle distribution significantly affects the electron transfer rates and the distribution of ion pairs formed by forward electron transfer, particularly at short times. In addition, finite solvent size affects the rate of relative diffusion between any...