Marcus'Electron Transfer Rate Revisited via a Rice-Ramsperger-Kassel-Marcus Analogue:A Uni ed Formalism for Linear and Nonlinear Solvation Scenarios  

作　　者：Yao Wang Yu Su Rui-Xue Xu Xiao Zheng YiJing Yan 

机构地区：[1]Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics and Synergetic Innovation Center of Quantum Information and Quantum Physics and Collaborative Innovation Center of Chemistry for Energy Materials(iChEM),University of Science and Technology of China,Hefei 230026,China

出　　处：《Chinese Journal of Chemical Physics》2021年第4期462-470,I0003,共10页化学物理学报（英文）

基　　金：This work was supported by the Ministry of Science and Technology of China(No.2017YFA0204904 and No.2016YFA0400904);the National Natural Science Foundation of China(No.21633006),and Anhui Initiative in Quantum Information Technologies.

摘　　要：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.

关 键 词：Electron transfer Marcus’rate formula Rice-Ramsperger-Kassel-Marcus theory Nonlinear solvation Fermi’s golden rule 

分 类 号：O642[理学—物理化学]