Reversible electron transfer dynamics in non‐Debye solvents
Reversible electron transfer dynamics in non‐Debye solvents
复制标题
非德拜溶剂中的可逆电子转移动力学
DOI：
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发表时间：
1992
期刊：
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通讯作者：
J. Rasaiah
中科院分区：
文献类型：
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作者：
J. Zhu;J. Rasaiah
早先[J. Chem. Phys. 95，3325（1991）]得到的描述德拜溶剂中可逆电子转移反应的耦合扩散-反应方程的一般解，由Sumi-Marcus自由能表面控制，被扩展到非德拜溶剂。这些解取决于反应坐标Δ（t）的时间相关函数，在德拜和非德拜溶剂的窄窗和宽窗极限以及德拜溶剂的慢反应和非扩散极限中是精确的。通解也预测了这些极限之间的行为，并且可以作为积分方程的解来获得。讨论了用有效弛豫时间求解该方程的迭代方法。阐明了Δ（t）与反应中间体Born溶剂化能时间关联函数S（t）的关系。
The general solutions obtained earlier [J. Chem. Phys. 95, 3325 (1991)] for the coupled diffusion‐reaction equations describing reversible electron transfer reactions in Debye solvents, governed by Sumi–Marcus free energy surfaces, are extended to non‐Debye solvents. These solutions, which depend on the time correlation function of the reaction coordinate Δ(t), are exact in the narrow and wide window limits for Debye and non‐Debye solvents and also in the slow reaction and non‐diffusion limits for Debye solvents. The general solution also predicts the behavior between these limits and can be obtained as the solution to an integral equation. An iterative method of solving this equation using an effective relaxation time is discussed. The relationship between Δ(t) and the time correlation function S(t) of Born solvation energy of the reacting intermediates is elucidated.