高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

二氯二氰基苯醌及其阴离子自交换电子转移反应的理论研究

齐琳琳, 王全德, 王静波, 傅克祥, 何福城, 李象远   

  1. 四川大学化工学院, 成都 610065
  • 收稿日期:2008-10-28 修回日期:1900-01-01 出版日期:2008-12-10 发布日期:2008-12-10
  • 通讯作者: 李象远

Theoretical Studies on Self-exchange Electron Transfer Between 2,3-Dicyano-5,6-dichloro-p-benzoquinone and Its Radical Anion

QI Lin-Lin, WANG Quan-De, WANG Jing-Bo, FU Ke-Xiang, HE Fu-Cheng, LI Xiang-Yuan*   

  1. College of Chemical Engineering, Sichuan University, Chengdu 610065, China
  • Received:2008-10-28 Revised:1900-01-01 Online:2008-12-10 Published:2008-12-10
  • Contact: LI Xiang-Yuan

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摘要： 基于非平衡溶剂化能的约束平衡方法和溶剂重组能的新表达式, 实现了电子转移反应溶剂重组能的数值解, 研究了二氯二氰基苯醌(DDQ)及其阴离子体系DDQ-之间的自交换电子转移反应. 考虑了DDQ与DDQ-分子以平行方式形成受体-给体络合物时的两种构型. 引入线性反应坐标, 计算了该反应在不同溶剂中的溶剂重组能. 基于两态变分模型得到了反应的电子耦合矩阵元. 根据电子转移动力学模型, 计算了该自交换电子转移反应的速率常数.

关键词: 非平衡溶剂化, 二氯二氰基苯醌, 电子转移, 溶剂重组能

Abstract: We studied the self-exchange electron transfer reaction between 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and its radical anion, on the basis of the non-equilibrium solvation theory in virtue of a constrained equilibrium state. Two different conformations of the parallel donor-acceptor complexes were considered. Using the new non-equilibrium solvation model combined with the linear reaction coordinate, we calculated the solvent reorganization energy in different solvents. The electronic coupling are obtained through the two-state model. The self-exchange electron transfer reaction rate constants in different solvents were calcu-lated and the results correlate well with the experimental values.

Key words: Non-equilibrium solvation, 2,3-Dicyano-5,6-dichloro-p-benzoquinone, Electron transfer, Solvent reorganization energy

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