Electric field dependence of the diabatic potential energy surface for gas-phase electron transfer O2O2− → O2−O2

At the level of 6–31G plus a set of sp diffuse functions, the structures of two nonlinear encounter complexes of O2O2− have been optimized. The influence of the external electric field (field strength F) upon the diabatic potential energy surfaces has been investigated. An electron-localized initial guess has been used to induce the UHF SCF calculation, and the F-dependent diabatic potential surfaces have been constructed. A simple model for the F-dependent rate constant of electron transfer has been proposed.