THEORETICAL-STUDIES ON THE INNER-SPHERE REORGANIZATION ENERGIES FOR THE SELF-EXCHANGE REACTIONS OF GAS-PHASE DIATOMIC-MOLECULES HA (A=MG, AL, SI, P, S, CL)

On the basis of the recently proposed accurate calculation scheme of t he inner-sphere reorganization energies (RE) of the reactants in gas-p hase electron-transfer xprocesses, the inner-sphere RE values for the AH + AH(+) (A = Mg, Al, Si, P, S, Cl) self-exchange systems are calcul ated in terms of an ab initio Hartree-Fock self-consistent-field MO me thod at different basis-set levels (6-31G*, 6-31+G**, DZ, and DZP). T he structural parameters involved are also determined via the perturba tion theory and the Dunham expansion of the Morse function and compare d with the experimental values. Dissociation energies are corrected by electron correlation at the MP2/6-31G level. Results of the inner-sp here REs obtained from different models via ab initio calculations for these systems discussed here are in full agreement with the correspon ding experimental data. (C) 1995 John Wiley & Sons, Inc.