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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (05): 577-584. 上一篇    下一篇

研究论文

CH3NO异构体及异构化反应机理的量子化学研究

杨丽娟1,3，李晓艳2，曾艳丽2，郑世钧2，孟令鹏*,2，赵毅1   

  1. (1华北电力大学环境科学与工程学院 保定 071003)
    (2河北师范大学化学与材料科学学院 石家庄 050016)
    (3华北电力大学科技学院 保定 071003)
  • 投稿日期:2010-05-13 修回日期:2010-10-10 发布日期:2010-11-01
  • 通讯作者: 赵毅 E-mail:hgxzy@sina.com,zhaoyi9515@163.com
  • 基金资助:

    国家自然科学基金项目;河北省自然科学基金;河北省教育厅基金项目;华北电力大学青年教师科研基金;河北师范大学科研基金

Quantum Chemical Study on the Isomers and Isomerization Reaction Mechanism of CH3NO

Yang Lijuan1,3 Li Xiaoyan2 Zeng Yanli2 Zheng Shijun2, Meng Lingpeng*,2 Zhao Yi1   

  1. (1 College of Environmental Science and Engineering, North China Electric Power University, Baoding 071003)
    (2 College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050016)
    (3 College of Science and Technology, North China Electric Power University, Baoding 071003)
  • Received:2010-05-13 Revised:2010-10-10 Published:2010-11-01

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在CCSD(T)/6-311＋＋G(d,p)//B3LYP/6-311＋＋G(d,p)水平上对CH3NO的异构体及各异构化反应机理进行了详细的理论研究. 包括CH3NO共找到了23种异构体, 这23种异构体间通过24个过渡态相互转化. 用振动频率分析证实了过渡态的真实性, 内禀反应坐标跟踪(IRC)计算验证了过渡态与各异构体的连接关系. 计算结果表明, 在CH3NO的各种异构体中, 分子骨架中存在N—C—O结构是最稳定的, 而C—O—N, C—N—O结构能量最高, 不稳定. 异构体间的异构化反应主要通过化学键的旋转, H迁移, C, N, O骨架的重组及包含上述两种机理的混合型机理等4种方式完成.

关键词: CH3NO, 异构化反应, 过渡态, 反应机理

The structures of CH3NO isomers and their isomerization have been investigated at CCSD(T)/ 6-311＋＋G(d,p)//B3LYP/6-311＋＋G(d,p) level. 23 isomers including CH3NO were found and they were linked by 24 transition states. The characterizations of the transition states are confirmed by vibration analysis. The intrinsic reaction coordinates (IRC) have been traced according to Fukui s theory and the connecting relationship of the transition states with the reactants and products was confirmed. The calculated results show that the isomers with N—C—O structure are the most stable, while those with C—O—N and C—N—O structures are not stable because of their high energies. The isomers transform to each other by the rotation of the chemical bond, the transfer of H atom, the reorganization of C, N and O skeleton and the mixed type reaction mechanism of above-mentioned.

Key words: CH3NO, isomerization, transition state, reaction mechanism

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