Ab initio study of the structural reorganization of AH 2 (A = B, C, N, O) molecules in a gaseous-phase electron transfer process

Abstract

Using self-exchange electron transfer (ET) as the basis, three scale methods and the ab initio compute the inner-sphere reorganization energy (RE) of redox couples participating in ET reactions in the gaseous phase. The parameters involved in the scale formulae were determined by using ab initio calculations at different HFSCF basis-set levels, and the results were compared with the experimental findings. The inner-sphere REs were calculated for the AH 2/AH + 2 (A = B, C, N and O) system. As an approximation the bond-angle coupling interaction constrast was neglected in building up the scale formulae via the function model; the reasonableness of this approximation is discussed. The results show that values obtained from ab initio calculations and using the most accurate theoretical scale method give the best agreement with values obtained with function scale methods.