AB-INITIO STUDY OF THE STRUCTURAL REORGANIZATION OF AH2 (A=B, C, N, O) MOLECULES IN A GASEOUS-PHASE ELECTRON-TRANSFER PROCESS

Using self-exchange electron transfer (ET) as the basis, three scale m ethods and the ab initio MO method were used to compute the inner-sphe re reorganization energy (RE) of redox couples participating in ET rea ctions in the gaseous phase. The parameters involved in the scale form ulae were determined by using ab initio calculations at different HFSC F basis-set levels, and the results were compared with the experimenta l findings. The inner-sphere REs were calculated for the AH2/AH2+ (A = B, C, N and O) system. As an approximation the bond-angle coupling in teraction constant was neglected in building up the scale formulae via the function model; the reasonableness of this approximation is discu ssed. The results show that values obtained from ab initio calculation s and using the most accurate theoretical scale method give the best a greement with values obtained with function scale methods.