Theoretical Study on the NO2＋NO2^— Electron Transfer Reaction

The NO2 NO2^- electron transfer reaction was studied with DFT-B3LYP method at 6-311 G^* basis set level for the eight selected structures:four species favor the structure of “head to head”.The geometry of transition state was obtained by the linear corrdinate method.Three parameters,non-adiabatic activation energy(Ead),coupling matrix element(Hif) and reorganization energy(λ) for electron transfer reaction can be calculated.According to the reorganization energy of the ET reaction,the values obtained from George-Griffith-Marcus (GGM) method(the contribution only from diagonal elements of force constant matrix) are larger than those obtained from Hessian matrix method(including the contribution from both diagonal and off-diagonal elements), which suggests that the coupling interactions between different vibrational modes are important to the inner-sphere reorganization energy for the ET reactions in gaseous phase.The value of rate constant was obtained by using above three activation parameters.

Theoretical Study on the NO_2+NO_2~- Electron Transfer Reaction