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化学学报
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化学学报 ›› 2004, Vol. 62 ›› Issue (20): 2015-2020. 上一篇    下一篇

研究论文

O原子与HNCO反应机理的量子化学及电子密度拓扑研究

王俊敏1, 曾艳丽1,2, 郑世钧1, 孟令鹏1   

  1. 1. 河北师范大学, 计算量子化学所, 石家庄, 050091;
    2. 中国科学院研究生院化学系, 北京, 100039
  • 投稿日期:2003-12-24 修回日期:2004-04-15 发布日期:2014-02-17
  • 通讯作者: 郑世钧,E-mail:sjzheng@mail.hebtu.edu.cn;Tel:0311-6263381 E-mail:sjzheng@mail.hebtu.edu.cn
  • 基金资助:
    河北省自然科学基金(No.B2004000147)资助项目.

Quantum Chemical and Topological Study on the Reaction Mechanism of O and HNCO Reaction

WANG Jun-Min1, ZENG Yan-Li1,2, ZHENG Shi-Jun1, MENG Ling-Peng1   

  1. 1. Insititue of Quantum Chemistry in College of Chemistry, Hebei Normal University, Shijiazhuang 050091;
    2. Department of Chemistry, Graduate School, Chinese Academy of Sciences, Beijing 100039
  • Received:2003-12-24 Revised:2004-04-15 Published:2014-02-17

PDF

393

被引次数

26

采用MP2(Full),B3LYP,QCISD/MP2和CCSD(T)/MP2方法在6-311G(d,p)水平上对O原子与HNCO反应的微观机理进行了理论研究.采用MP2(Full)和B3LYP对反应位能面上的各驻点进行几何构型的全优化,振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系.四种方法计算得到了四个反应通道的反应活化能.研究表明,O原子进攻HNCO中的H原子为反应的主要反应通道,该通道中形成了两个分子复合物,电子密度拓扑分析表明这两个分子复合物均为氢键复合物.

关键词: 反应机理, 反应通道, 电子密度拓扑分析, 氢键复合物

The reaction mechanism of O with HNCO has been investigated by using MP2(full), B3LYP, QCISD/MP2 and CCSD(T)/MP2 methods at 6-311g(d,p) level. The geometries of various stationary points were optimized by MP2 and B3LYP methods. Intermediates and transition states were confirmed by vibration analysis. The reaction active energies of four channels were attained by four methods. It was found that the channel one is the main reaction channel and there are two molecular hydrogen-bond complexes in this channel. Topological analysis of electronic density supported that the two complexes are hydrogen-bonded ones.

Key words: reaction mechanism, reaction channel, topological analysis of electronic density, hydrogen2bond complex