物理化学学报 >> 2001, Vol. 17 >> Issue (02): 107-110.doi: 10.3866/PKU.WHXB20010203

研究论文 上一篇    下一篇

F＋Cl2->ClF＋Cl和Cl′F＋Cl->Cl′＋ClF的反应机理

王遵尧;肖鹤鸣;李金山   

  1. 南京理工大学化学系,南京　210094;盐城工学院化工系,盐城 　224003
  • 收稿日期:2000-05-22 修回日期:2000-07-17 发布日期:2001-02-15
  • 通讯作者: 肖鹤鸣 E-mail:xiao@mail.njust.edu.cn

Mechanism of the Reactions F＋Cl2->ClF ＋Cl and Cl′F＋Cl->Cl′＋ClF

Wang Zun-Yao;Xiao He-Ming;Li Jin-Shan   

  1. Department of Chemistry,Nanjing University of Science and Technology,Nanjing　210094;Department of Chemical Engineering,Yancheng Institute of Technology,Yancheng　224003
  • Received:2000-05-22 Revised:2000-07-17 Published:2001-02-15
  • Contact: Xiao He-Ming E-mail:xiao@mail.njust.edu.cn

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摘要： 用密度泛函理论(DFT)B3LYP方法,取6311G基组,计算研究了F＋Cl2ClF＋Cl的反应机理.求得1个线形和2个三角形过渡态,反应能垒分别为1.24、46.37和105.09kJ•mol－1；同时发现F以∠FClCl为10～20°（或 120～160°）进攻Cl2时,反应无能垒.此外,求得对称反应Cl′F＋ClCl′＋ClF的能垒为40.57 kJ•mol－1的1个过渡态.

关键词: 卤素, 氟, 氯, 密度泛函理论, 过渡态, 反应机理

Abstract: The reaction F＋Cl2ClF＋Cl was investigated by density functional theory (DFT) at the B3LYP/6311G level. The reaction can occur via a linear transition states with a reaction barrier of 1.24 kJ•mol－1,and can also via two triangle transition states with reaction barriers of 46.37 and 105.09 kJ•mol1,respectively.In addition,we also found that there is no energy barrier when F attacks Cl2 with an angle ∠FClCl of 10－20°(or 160－120°).The energy barrier of the symmetrical reaction Cl′F＋ClCl′＋ClF was calculated to be 40.57 kJ•mol1.All transition states were confirmed by vibrational analyses and the possible reaction paths were obtained by IRC calculations.

Key words: Halogen, Fluorine, Chlorine, Density functional theory, Transition state