高等学校化学学报 ›› 1999, Vol. 20 ›› Issue (6): 945.

• 论文 • 上一篇    下一篇

溶液中M(H2O)62+/3+(M=V,Cr,Mn,Fe,Co)自交换电子转移体系内层重组能和活化能的理论研究

张冬菊1, 李林尉2, 冯大诚1, 步宇翔1, 刘成卜1   

  1. 1. 山东大学理论化学研究室, 济南 250100;
    2. 聊城师范学院化学系, 聊城 252052
  • 收稿日期:1998-06-06 出版日期:1999-06-24 发布日期:1999-06-24
  • 通讯作者: 张冬菊,女,33岁,博士研究生.
  • 作者简介:张冬菊,女,33岁,博士研究生.
  • 基金资助:

    国家自然科学基金(批准号:29873025)资助课题

Theoretical Study of the Innersphere Reorganization Energy and Activation Energy of Selfexchange Electron Transfer Reaction for M(H2O)62+/3+(M=V, Cr, Mn, Fe and Co) Systems

ZHANG Dong-Ju1, LI Lin-Wei2, FENG Da-Cheng1, BU Yu-Xiang1, LIU Cheng-Bu1   

  1. 1. Institute of Theoretical Chemistry, Shandong University, Jinan, 250100;
    2. Department of Chemistry of Liaocheng Normal College, Liaocheng, 252052
  • Received:1998-06-06 Online:1999-06-24 Published:1999-06-24

摘要: 通过建立电子转移过程的活化模型和重组模型,提出了用量子化学从头算方法研究电子转移过程内层重组能和活化能的新方法.在UMP2/6-311G水平上获得了5对过渡金属水合离子体系M(H2O)62+/3+(M=V,Cr,Mn,Fe,Co)自交换反应的内层重组能和活化能,获得了与Marcus电子转移理论相一致的结果.

关键词: 电子转移, 自交换反应, 活化模型, 重组模型, 从头算

Abstract: The activation model and reorganization model of electron transfer process are presented respectively in terms of the definitions of activation energy and reorganization energy. A new method is presented for calculating the innersphere activation energy and reorganization energy of selfexchange electron transfer reaction between transition metal complexes in aqueous solution by using Ab initio calculation. Ab initio calculations are applied to low-lying state M(H2O)62+/3+(M=V, Cr, Mn, Fe and Co) system at the UMP2 level using 6-311G basis set. The innersphere reorganization energy and activation energy of these reaction systems in the electron process are obtained and are in good agreement with prediction of Marcus electron transfer theory.

Key words: Electron transfer, Self-exchange reaction, Activation model, Reorganization model, Ab initio

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