Calculation Reorganize Energy of Electron Transfer Reaction in Benzene Nitride

This paper presents a new theoretical model for accurately calculating reorganization energy for electron transfer reactions. The process of electron transfer is divided into six steps, and the energy change of every step can be calculated byab initio. The structure of reactant and transition states in benzene nitride reactions is optimized on the level of CISD/6-31GusingGaussian 94. The inner-sphere and out-sphere reorganization energy of self-exchange reactions ArH+ArH+→ArH++ArH, O2++NO2→NO2+NO2+ and NO++NO→NO+NO+is obtained in terms of the proposed reorganization model. The reorganization energy of cross electron transfer reaction ArH+NO+→ArH++NO and NO2++NO→NO2+NO+is also obtained. The comparison of the theoretical values and the experimental values for the reorganization energy indicates that the inner-sphere reorganization energy of reactions inNO2++NO2→NO2+NO2+is larger than that in NO++NO→NO+NO+. While there exists little opportunity of electron transfersteps usingNO2+as an oxidizing agent, it is more possible that NO+ can be used as an oxidizing agent in the reaction of benzene because of the activation energy in proportion to the reorganization energy.