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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (11): 1013-1017. 上一篇    下一篇

研究论文

CH3O与ClO双自由基反应机理的量子化学研究

赵岷1 2，刘朋军1，常鹰飞1，孙昊1，苏忠民1，王荣顺*1   

  1. (1东北师范大学化学学院 功能材料化学研究所 长春 130024)
    (2渤海大学化学化工学院 锦州 121000)
  • 投稿日期:2004-06-23 修回日期:2005-01-28 发布日期:2010-12-10
  • 通讯作者: 王荣顺

Quantum Chemical Investigation of the Reaction Mechanism of CH3O with ClO

ZHAO Min1,2, LIU Peng-Jun1, CHANG Ying-Fei1, SUN Hao1, SU Zhong-Min1, WANG Rong-Shun*1   

  1. (1 Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024)
    (2 College of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121000)
  • Received:2004-06-23 Revised:2005-01-28 Published:2010-12-10

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在QCISD(T)/6-311＋G(d,p)//B3LYP/6-311＋G(3df,3pd)水平上, 对CH3O与ClO双自由基反应进行了理论研究. 结果表明, 该反应共有三个反应通道, 产物分别为HOCl＋CH2O, CH2O2＋HCl和CH3Cl＋O2(1Δ). 不论从动力学角度, 还是从热力学角度看, 形成产物HOCl＋CH2O的通道均是最有利的, 因此为主要反应通道, 这与实验观察到的结果是一致的.

关键词: CH3O, ClO, 反应机理, 过渡态

The mechanism for the double radicals reaction of CH3O with ClO has been investigated theoretically at QCISD(T)/6-311＋G(d,p)//B3LYP/6-311＋G(3df,3pd) level. The results show that the reaction has three channels, yielding the products of HOCl＋CH2O, CH2O2＋HCl and CH3Cl＋O2(1Δ), respectively. The route to produce HOCl＋CH2O was most favorable no matter whether it was considered from the viewpoint of kinetics or thermodynamics. Thus, the channel producing HOCl＋CH2O is the main one in agreement with experiment.

Key words: CH3O, ClO, reaction mechanism, transition state