Internal Reorganization Energy Contributed by Torsional Motion in Electron Transfer Reaction between Biphenyl and Biphenyl Anion Radical

• 来源期刊: 中国化学（英文版）
• 年，卷（期）: 2002,（10）
• 页码范围: 963-967
• 页数: 5页
• 语种: 英文

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 reoganization energy.Based on the above model, an estimation of pure torsional reorganization energy λt,p with an approximation of λt,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 estinate the reorganization energy contributed by pure torsional motion of Bp.