摘要
The NO_2 + NO_2^- electron transfer reaction was studied with DFT-B3LYPmethod at 6-311 + G~* basis set level for the eight selected structures: four species favor thestructure of 'head to head'. The geometry of transition state was obtained by the linear coordinatemethod. Three parameters, non-adiabatic activation energy (E_(ad)), coupling matrix element (H_(if))and reorganization energy (λ) for electron transfer reaction can be calculated. According to thereorganization 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 thoseobtained from Hessian matrix method (including the contribution from both diagonal and off-diagonalelements), which suggests that the coupling interactions between different vibrational modes areimportant to the inner-sphere reorganization energy for the ET reactions in gaseous phase. The valueof rate constant was obtained by using above three activation parameters.
The NO_2 + NO_2^- electron transfer reaction was studied with DFT-B3LYPmethod at 6-311 + G~* basis set level for the eight selected structures: four species favor thestructure of 'head to head'. The geometry of transition state was obtained by the linear coordinatemethod. Three parameters, non-adiabatic activation energy (E_(ad)), coupling matrix element (H_(if))and reorganization energy (λ) for electron transfer reaction can be calculated. According to thereorganization 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 thoseobtained from Hessian matrix method (including the contribution from both diagonal and off-diagonalelements), which suggests that the coupling interactions between different vibrational modes areimportant to the inner-sphere reorganization energy for the ET reactions in gaseous phase. The valueof rate constant was obtained by using above three activation parameters.
基金
ProjectsupportedbytheNaturalScienceFoundationofShandongProvince (No .Y99B0 1)
theNationalKeyLaboratoryFoundationofCrystalMaterial(No.S0 1A0 2 )andtheNationalNaturalScienceFoundationofChina (No .2 96 730 5 ) .
