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 shown that for the non-adiabatic crossing regime the transitions take place in a region which is larger than the strong interaction region. In the case of dynamical motion a qualitative difference in the character of transitions at non-adiabatic and adiabatic regimes is demonstrated. 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 relaxation are analyzed. Limitations on the applicability of the balance approximation and diffusional model for the description of non-adiabatic electron transfer are discussed.