Linear response in theory of electron transfer reactions as an alternative to the molecular harmonic oscillator model

摘要: The effect of solvent fluctuations on the rate electron transfer reactions is considered using linear response theory and a second-order cumulant expansion. An expression obtained for constant in terms dielectric function solvent. It shown thereby that this expression, which usually derived molecular harmonic oscillator ("spin-boson") model, valid not only approximately systems such as solids but also strongly molecularly anharmonic polar solvents. derivation relatively simple alternative to one based quantum field theoretic techniques. system inhomogeneity due presence solute molecule now included. given generalizing frequency space mechanically analogue an electrostatic result relating reorganization free energy difference two hypothetical [J. Chem. Phys. 39, 1734 (1963)]. latter has been useful adapting specific models literature problems, present extension can be expected have similar utility.