物理化学学报 >> 2005, Vol. 21 >> Issue (02): 166-172.doi: 10.3866/PKU.WHXB20050211

研究论文 上一篇    下一篇

ClO与ClO自由基反应机理及电子密度拓扑分析

周俊红;曾艳丽;孟令鹏;郑世钧   

  1. 河北师范大学计算量子化学研究所,石家庄 050091
  • 收稿日期:2004-06-30 修回日期:2004-09-14 发布日期:2005-02-15
  • 通讯作者: 郑世钧 E-mail:sjzheng@mail.hebtu.edu.cn

Reaction Mechanisms and Topological Studies of Electron Density on the Reaction of ClO and ClO Radical

ZHOU Jun-Hong;ZENG Yan-Li;MENG Ling-Peng;ZHENG Shi-Jun   

  1. Institute of Computational Quantum Chemistry, College of Chemistry, Hebei Normal University, Shijiazhuang 050091
  • Received:2004-06-30 Revised:2004-09-14 Published:2005-02-15
  • Contact: ZHENG Shi-Jun E-mail:sjzheng@mail.hebtu.edu.cn

摘要: 利用密度泛函理论对ClO与ClO自由基反应机理进行了深入理论探讨,在B3LYP/6-311++G(3df)水平上对该反应体系的反应物、中间体、过渡态及产物进行了几何构型优化,对反应通道进行了IRC(内禀反应坐标)路径解析,计算了沿各反应通道的能垒和离解能,并进行了零点能校正.从量子拓扑学的角度,对反应通道IRC途径上一些重要点进行了电子密度拓扑分析,讨论了反应过程中化学键的断裂、生成以及键的变化规律,找到了反应途径的能量过渡态和结构过渡态.

关键词: 密度泛函理论, ClO自由基, 反应机理, 能量过渡态(ETS), 结构过渡态(STS)

Abstract: On the basis of density functional theory, the reaction paths for ClO and ClO have been studied. The reactants, intermediates, transition states, and products have been optimized at the B3LYP/6-311++(3df) level. IRC (intrinsic reaction coordinate) calculations have also been processed. The energies with zero point energy correction have been calculated, the characters of the major critical points have been discussed by topological analysis of the electronic density, and the chemical bonds have been discussed. The energy transition states (ETS) and structure transition states (STS) have been found.

Key words: Density functional theory, ClO radical, Reaction mechanism, Energy transition state, Structure transition state