一种用于氢原子转移/质子耦合电子转移的简单马库斯理论类型模型。
A Simple Marcus-Theory Type Model for Hydrogen Atom Transfer/Proton-Coupled Electron Transfer.
作者信息
Mayer James M
机构信息
Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195-1700
出版信息
J Phys Chem Lett. 2011;2:1481-1489. doi: 10.1021/jz200021y.
Abstract
Hydrogen atom transfer reactions are the simplest class of proton-coupled electron transfer (PCET) processes. These reactions involve transfer of one electron and one proton from one reagent to another, in the same kinetic step: XH + Y → X + HY. A predictive model for these reactions based on the Marcus cross relation is described. The model predicts rate constants within one or two orders of magnitude in most cases, over a very wide range of reactants and solvents. This remarkable result implies a surprising generality of the additivity postulate for the reaction intrinsic barriers, and a smaller role for the quantum mechanical details of the proton and electron transfers.
摘要
氢原子转移反应是质子耦合电子转移（PCET）过程中最简单的一类。这些反应涉及在同一动力学步骤中，一个电子和一个质子从一种试剂转移到另一种试剂：XH + Y → X + HY。本文描述了基于马库斯交叉关系的这些反应的预测模型。在大多数情况下，该模型在非常广泛的反应物和溶剂范围内，能将速率常数预测在一到两个数量级之内。这一显著结果意味着反应本征势垒的加和假设具有惊人的普遍性，并且质子和电子转移的量子力学细节所起的作用较小。
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