RADIATIVE AND NONRADIATIVE ELECTRON-TRANSFER IN CONTACT RADICAL-ION PAIRS

The relationship between radiative and nonradiative electron transfer is explored for return electron transfer processes in the contact radi cal-ion pairs formed by excitation of ground state CT complexes. Using a conventional nonadiabatic theory of electron transfer, absolute rat e constants for nonradiative return electron transfer, varying over mo re than two orders of magnitude, can be predicted from information obt ained from analyses of the corresponding radiative processes. The effe cts of solvent polarity, driving force and molecular dimension on the rates of nonradiative return electron transfer are studied.