摘要
Concerning the theoretical estimation of internal reorganization energy contributed by the tortional motion between biphenyl and biphenyl anion radical, direct calculation of self-exchange electron transfer reaction was investigated. With the introduction of a proper average bond length and angle parameters <bond Bp>, a multiple step relaxation Nelson method was developed to deal with the torsional reorganization energy. Based on the above model, an estimation of pure torsional reorganization energy λ t,p with an approximation of λ t,1 was achieved. The results of 0.140 and 0.125 eV of torsional reorganization energy for a cross-reaction at the levels of 4-31G and HP/DZP, respectively, are in good agreement with the value of 0.13 eV obtained by Miller et al. from the rate measurements. This implies the efficiency and validity of our method to estimate the reorganization energy contributed by pure torsional motion of Bp.
Concerning the theoretical estimation of internal reorganization energy contributed by the tortional motion between biphenyl and biphenyl anion radical, direct calculation of self-exchange electron transfer reaction was investigated. With the introduction of a proper average bond length and angle parameters <bond Bp>, a multiple step relaxation Nelson method was developed to deal with the torsional reorganization energy. Based on the above model, an estimation of pure torsional reorganization energy λ t,p with an approximation of λ t,1 was achieved. The results of 0.140 and 0.125 eV of torsional reorganization energy for a cross-reaction at the levels of 4-31G and HP/DZP, respectively, are in good agreement with the value of 0.13 eV obtained by Miller et al. from the rate measurements. This implies the efficiency and validity of our method to estimate the reorganization energy contributed by pure torsional motion of Bp.
基金
ProjectsupportedbytheChineseResearchEndowmentofHui ChunChinandTsung DaoLee
