物理化学学报 >> 2000, Vol. 16 >> Issue (09): 855-859.doi: 10.3866/PKU.WHXB20000918

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Co(H2O)62+/3+体系电子转移反应动力学的理论研究

张冬菊, 胡海泉, 刘永军, 步宇翔, 刘成卜   

  1. 山东大学理论化学研究所，济南 250100
  • 收稿日期:2000-01-24 修回日期:2000-04-13 发布日期:2000-09-15
  • 通讯作者: 张冬菊

Theoretical Study of Self-Exchange Electron Transfer Renctions for Co(H2O)62+/3+ System

Zhang Dong-Ju, Hu Hai-Quan, Liu Yong-Jun, Bu Yu-Xiang, Liu Cheng-Bu   

  1. Institute of Theoretical Chemistry,Shangdong University,Jinnan 250100
  • Received:2000-01-24 Revised:2000-04-13 Published:2000-09-15
  • Contact: Zhang Dong-Ju

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关键词: 电子转移, 活化模型, 微扰理论, 从头算

Abstract:

A theoretical scheme is presented which is based on an activation model for calculating the rate of the electron- exchange reaction between transition metal complexes in aqueous solution and applies to Co(H2O)6 2+/3+ electron transfer system. The activation parameter and activation energy of the system are obtained via the activation model. The slopes of the potential energy surfaces (curves) of the reacting system at the separated reactants are calculated from the fitted potential energy curves. The coupling matrix element is determined by using the perturbation theory and numerical integral method. Theoretical rate constants are obtained for the system at both UHF/6-311G and UMP2/6-311G levels. The agreement of the theoretical results with experimetal values is excellent. This fact indicates the scheme proposed is feasible and accurate in studying the self- exchange eletron transfer reaction.

Key words: Electron-transfer, Activation model, Perturbation theory, Ab initio