Hammes-Schiffer S
Department of Chemistry, The Pennsylvania State University, 152 Davey Laboratory, University Park, PA 16802, USA.
Acc Chem Res. 2001 Apr;34(4):273-81. doi: 10.1021/ar9901117.
This Account presents a theoretical formulation for proton-coupled electron transfer reactions. The active electrons and transferring protons are treated quantum mechanically, and the free energy surfaces are obtained as functions of collective solvent coordinates corresponding to the proton and electron transfer reactions. Rate expressions have been derived in the relevant limits, and methodology for including the dynamical effects of the solvent and protein has been developed. This theoretical framework allows predictions of rates, mechanisms, and kinetic isotope effects for proton-coupled electron transfer reactions.
本综述介绍了质子耦合电子转移反应的理论公式。活性电子和转移质子采用量子力学处理，自由能面是作为与质子和电子转移反应相应的集体溶剂坐标的函数而获得的。在相关极限下推导了速率表达式，并开发了纳入溶剂和蛋白质动力学效应的方法。该理论框架能够预测质子耦合电子转移反应的速率、机理和动力学同位素效应。
