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 so...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.展开更多
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.
文摘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.
