高等学校化学学报

高等学校化学学报 ›› 1995, Vol. 16 ›› Issue (5): 775.

• 论文 • 上一篇    下一篇

非绝热电子转移动力学模型及O2O2-→O2-O2研究

李象远, 田安民, 何福城, 鄢国森   

  1. 四川联合大学化学系, 成都, 610064
  • 收稿日期:1994-06-01 修回日期:1994-10-06 出版日期:1995-05-24 发布日期:1995-05-24
  • 通讯作者: 李象远,男,36岁,教授.
  • 作者简介:李象远,男,36岁,教授.
  • 基金资助:

    国家自然科学基金

A Kinetic Model of Nonadiabatic Electron Transfer andIts Application to O2O2-→O2-O2

LI Xiang-Yuan, TIAN An-Min, HE Fu-Cheng, YAN Guo-Sen   

  1. Department of Chemistry, Sichuan Union University, Chengdu, 610064
  • Received:1994-06-01 Revised:1994-10-06 Online:1995-05-24 Published:1995-05-24

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摘要： 描述非绝热电子转移的半经典模型,揭示了对称双势阱非绝热电子转移的过渡态能垒与Arrhenius活化能关系的一些新特征。在4-31G加负离子sp弥散函数水平上优化了O2O2-→O2-O2共线反应的反应物、络合物和过渡态的构型,成功地进行了电子定域UHF诱导自洽场计算,获得电子转移矩阵元VAB为7.0kJ/mol,活化能垒Ec为28.4kJ/mol,300K时反应速率常数k为9.2×108/s,讨论了理论模型及计算结果。

关键词: 非绝热电子转移, 弱偶合, 电子转移矩阵元, Landau-Zener模型

Abstract: the semiclassical model for nonadiabatic electron transfer has been described.Some new features for the relations between the energy barrier (Ec) at the crossing point and the activation energy(Ea) in the Arrhenius rate law have been revealed.The complex, reac tants, and the transition state for the colinear reaction have been optimized at 4-31G augmented with a set of anion diffuse functions. After a successful UHF SCFcalcula tion due to a electron-located initial guess, the authors have obtained the electron transfer matrix element VAB=7. 0 kJ/mol, the energy barrier Ec=28. 4 kJ/mol, the rate constant k=9. 2×108/s at 300 K. The discussions for the theoretical model and the calculated results have been made.

Key words: Nonadiabatic electron transfer, Weak coupling, Electron transfer matrix ele ment, Landau-Zener model

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