NONADIABATIC AND ADIABATIC REGIMES OF TRANSITIONS BETWEEN INTERSECTING TERMS - APPLICATIONS TO ELECTRON-TRANSFER

A qualitative analysis of different crossing regimes and the character of transitions between intersecting terms has been performed. It is s hown that for the non-adiabatic crossing regime the transitions take p lace in a region which is larger than the strong interaction region. I n the case of dynamical motion a qualitative difference in the charact er of transitions at non-adiabatic and adiabatic regimes is demonstrat ed. It is shown that effects related to diffusional re-crossing of the transition region are responsible for the formation of the strong non -adiabatic transfer (solvent-controlled transfer in the non-adiabatic regime). A balanced description of the transitions in the diffusional adiabatic crossing regime is elaborated and the effects of velocity re laxation are analyzed. Limitations on the applicability of the balance approximation and diffusional model for the description of non-adiaba tic electron transfer are discussed.