高等学校化学学报

高等学校化学学报 ›› 1991, Vol. 12 ›› Issue (2): 219.

• 论文 • 上一篇    下一篇

化学反应的内禀反应坐标法(Ⅷ)--甲基叠氮热解反应的反应路径解析

陈彬, 赵成大, 傅强, 李英伟   

  1. 东北师范大学化学系, 130024
  • 收稿日期:1989-01-16 出版日期:1991-02-24 发布日期:1991-02-24
  • 通讯作者: 赵成大
  • 基金资助:

    国家自然科学基金

The IRC Method in Chemical Reactions (Ⅷ)--Reaction Ergodography for the Pyrolysis of Methyl Azide

Chen Bin, Zhao Cheng-da, Fu Qiang, Li Ying-wei   

  1. Department of Chemistry, Northeast Normal University, Changchun, 130024
  • Received:1989-01-16 Online:1991-02-24 Published:1991-02-24

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摘要： 采用内禀反应坐标法完成了对甲基叠氮热解反应途径的微观动力学解析.结果表明甲基叠氮的热解是以伴随N2消除后发生1,2-H迁移的协同方式完成的,属协同的非同步反应,此机制可解释(H3C)nH3-nC-N3(n=0～2)烷基叠氮系列热解温度的光电子能谱结果.

关键词: 内禀反应坐标, 从头算, 热解机理, 甲基叠氮

Abstract: The ab initio calculations were performed on the reaction ergodography for the pyrolysis of methyl azide by the Intrinsic Reaction Coordinate (IRC) method. The potential energy hypersurface and transition state structure were determined at RHF/4-31G level. The IRC analysis indicates that the pyrolysis of methyl azide occured through a 1,2-H shift coupled to N2elimination, but the N2elim-ination is prior to the 1,2-H shift. That is to say, such a reaction process is concerted but nonsyn-chronous. This mechanism can well explain the temperature-dependence of pyrolysis of alkyl azides (H3C)2H3-nC-N3(n=0-2) determined by PEspectra.

Key words: IRC, ab initio, Pyrolysis mechanism, Methyl azide

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