论文标题
Marcus的电子转移率通过Rice-Ramsperger-Kassel-Marcus类似物重新审视：线性和非线性溶剂化场景的统一形式主义
Marcus' electron transfer rate revisited via a Rice-Ramsperger-Kassel-Marcus analogue: A unified formalism for linear and nonlinear solvation scenarios
论文作者
论文摘要
在R. A. Marcus的开创性工作中，研究了对电子转移（ET）过程的溶剂化效应，从而产生了著名的非绝热ET速率公式。在这项工作中，基于热力学溶剂溶液的分析，我们对Marcus的公式进行了有关稻米 - ramsperger-kassel-kassel-marcus（RRKM）理论的公式。有趣的是，获得的RRKM类似物恢复了在线性溶剂化情况下的原始MARCUS的速率，也适用于非线性溶剂化场景，其中存在多重曲线{溶解电势的交叉。可行的，我们重新审视了相应的费米的黄金法则结果，并对这项工作中提出的RRKM类似物进行了一些批判性评论。为了说明，我们根据身体支持的描述符来考虑二次溶剂化场景。
In the pioneering work by R. A. Marcus, the solvation effect on electron transfer (ET) processes was investigated, giving rise to the celebrated nonadiabatic ET rate formula. In this work, on the basis of the thermodynamic solvation potentials analysis, we reexamine Marcus' formula with respect to the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Interestingly, the obtained RRKM analogue, which recovers the original Marcus' rate that is in a linear solvation scenario, is also applicable to the nonlinear solvation scenarios, where the multiple curve{crossing of solvation potentials exists. Parallelly, we revisit the corresponding Fermi's golden rule results, with some critical comments against the RRKM analogue proposed in this work. For illustration, we consider the quadratic solvation scenarios, on the basis of physically well-supported descriptors.
