高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (5): 810.

• 研究论文 • 上一篇    下一篇

非金属氧化-还原对MO2/MO2-(M=N,S,Cl)的电子转移反应动力学

张冬菊1, 庄炳游2, 刘永军1, 胡海泉1, 刘成卜1   

  1. 1. 山东大学理论化学研究所, 济南 250100;
    2. 潍坊学院化学系, 潍坊 261043
  • 收稿日期:2000-03-15 出版日期:2001-05-24 发布日期:2001-05-24
  • 通讯作者: 张冬菊(1964出生),女,博士,讲师,从事分子反应动力学研究.E-mail:lyzhdj@jn-public.sd.cninfo.net E-mail:lyzhdj@jn-public.sd.cninfo.net
  • 基金资助:

    国家自然科学基金(批准号:29873025);山东省自然科学基金资助

Dynamic Study of the Electron Transfer Reaction for Non-metal Redox Couples of 0/1-Type

ZHANG Dong-Ju1, ZHUANG Bing-You2, LIU Yong-Jun1, HU Hai-Quan1, LIU Cheng-Bu1   

  1. 1. Institute of Theoretical Chemistry, Shandong University, Jinan 250100, China;
    2. Department of Chemistry, Weifang College, Weifang 261043, China
  • Received:2000-03-15 Online:2001-05-24 Published:2001-05-24

摘要: 以Marcus-Hush电子转移理论为基础,提出了用量子化学密度泛函方法研究自交换和异交换电子转移反应的理论方案.在DFTB3LYP/6-311+G(2D)水平上研究了溶液中NO2/NO2-,SO2/SO2-和ClO2/ClO2-等3个氧化-还原对的自交换以及它们之间的6个交叉电子转移反应的动力学性质,获得了与实验较为一致的结果.

关键词: 电子转移, 活化能, 重组能, 速率常数, 密度泛函理论

Abstract: Atheoretical scheme is presented to study the dynamics of the self exchange reactions and cross-reactions for the several bent triatomic species of 0/1-type (NO2/NO2-, SO2/SO2-, ClO2/CLO2-). The values of the inner-sphere reorganization energy and activation energy are calculated by using Nelson's reoganization model with the results of density functional calculations. The values of the solvent reorganization energy are obtained by the dielectric continuum model of the Marcus Thery and by requesting a gas phase molecular volume calculation in Gaussian94 program package. The rate constants of the three self exchange reactions (NO2/NO2-, SO2/SO2-, ClO2/CLO2-) and six cross reactions (NO2/SO2-, NO2-/SO2, SO2-/CLO2-, SO2/CLO2-, NO2/CLO2-, NO2-/ClO2) are obtained by the relative and absolute Marcus Hush theories. The theoretical results are compared with the experimental findings or the values from literature and better agreements are fornd.

Key words: Electron transfer, Activation energy, Reorganization energy, Rate constant, Density functional theory

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