Molecular solvent-dynamical effects on activated electron-transfer kinetics: How important is solvent friction?

摘要: Abstract The likely extent of retardation exerted by solvent friction upon the rates activated electron-transfer (ET) processes is explored and evaluated with reference to some extant solvent-dependent data for metallocene ET self exchanges. Barrier-crossing frequencies extracted from experimental kinetic barrier suitably adiabatic reactions are compared inertial (i.e. zero-friction limit) as estimated currently available analytic expressions. additional rate seen in passing low-friction ostensibly strongly overdamped solvents, deduced this manner, be muted substantially comparison predictions conventional Debye-continuum approaches, although following a functionality that nevertheless roughly accord latter. importance more rapid dynamics associated short-range (molecular) solvation addressed light these findings.