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

摘要

This article presents an application of the accurate calculation scheme proposed recently for the inner-sphere reorganization energies of molecules of the type AH(2) (A = Al, Si, P, and S). A reasonable extension has been made. The inner-sphere reorganization energies for the title 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 parameters are also determined. These calculated results have been calibrated by comparing optimized molecular geometrical parameters and corresponding energy properties with the experimental findings or other theoretical values. An approximation, in which the contribution from the bond length-bond angle to the potential energy surface is neglected, is adopted in constructing the calculation formulas via the function model. Its adequacy is discussed. Agreement among different calculation schemes is analyzed. (C) 1995 John Wiley and Sons, Inc. [References: 59]