Solvation Structure in the Time Resolved Stokes Shift and Adiabatic ElectronTransfer

摘要

There is an important connection between the time resolved Stokes shift of achromophore in a polar solvent and the dynamical contribution to electron transfer reactions. We present a microscopic theory of the time resolved Stokes shift of a chromophore in a polar solvent which incorporates both non-Debye dielectric relaxation and solvation shell structure, then apply it to the Sparpaglione-Mukamel theory of electron transfer reactions. We find that molecular effects can dramatically affect the rate of reaction. Moreover, we find that when translational motion is fast compared to rotational motion, dielectric continuum theory gives a good approximation to the reaction rate. Four wave mixing and solvation dynamics, Stokes shift, femtosecond spectroscopy.