THE INNER-SPHERE REORGANIZATION ENERGIES FOR AH(2)-)) (A=AL, SI, P, S) ELECTRON SELF-EXCHANGE REACTIONS IN ELECTRON-TRANSFER PROCESSES FROMAB-INITIO CALCULATIONS(AH(2)(+()

This article presents an application of the accurate calculation schem e proposed recently for the inner-sphere reorganization energies of mo lecules of the type AH(2) (A = Al, Si, P, and S). A reasonable extensi on has been made. The inner-sphere reorganization energies for the tit le thermal electron self-exchange reactions are calculated in terms of ab initio MO self-consistent field method (HFSCF) at different basis- set levels (6-31G*, 6-31 + G**, DZ, and DZP) and the involved paramet ers are also determined. These calculated results have been calibrated by comparing optimized molecular geometrical parameters and correspon ding energy properties with the experimental findings or other theoret ical values. An approximation, in which the contribution from the bond length-bond angle to the potential energy surface is neglected, is ad opted in constructing the calculation formulas via the function model. Its adequacy is discussed. Agreement among different calculation sche mes is analyzed. (C) 1995 John Wiley and Sons, Inc.