物理化学学报 >> 1999, Vol. 15 >> Issue (04): 308-312.doi: 10.3866/PKU.WHXB19990405

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丙烯热反应生成甲基环戊烷的理论探讨

何丽针, 陈光巨, 刘若庄   

  1. 首都师范大学化学系,北京 100875
  • 收稿日期:1998-07-08 修回日期:1998-09-24 发布日期:1999-04-15
  • 通讯作者: 刘若庄

Investigation of the Thermal Reaction of Propene Forming Methylcyclopentane

He Li-Zhen, Chen Guang-Ju, Liu Ruo-Zhang   

  1. Department of Chemistry,Beijing Normal University,Beijing 100875
  • Received:1998-07-08 Revised:1998-09-24 Published:1999-04-15
  • Contact: Liu Ruo-Zhang

摘要:

在UHF/3-21G水平上,应用从头算分子轨道法和能量梯度技术,并用M?ller-Plesset二级微扰理论对能量进行了相关能校正,研究了丙烯在800K热反应形成甲基环戊烷的反应机理.求得该反应分三步进行:(1)两分子丙烯相互作用产生1,4-双自由基中间体;(2)1,4-双自由基中间体经氢迁移过程生成1,5-双自由基中间体;(3)1,5-双自由基中间体闭环形成甲基环戊烷.理论计算所得的机理与实验工作者推测一致.

关键词: 丙烯, 甲基环戊烷, 从头算分子轨道法, UMP

Abstract:

 The mechanism of the thermal reaction(800K/4.00-26. 66kPa) of propene producing methylcyclopentane has been studied theorecally by ab initio MO method at the level of UMP/ 3-21G. The results show that it is a three-step biradical reaction with L4-biradical and 1, 5-biradical as intermediates in sequence. The reaction pathway found in this article confirms the mechanism proposed by experimentalists.

Key words: Propene, Methylcyclopentane, Ab initio MO method, UMP