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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (18): 2039-2045. 上一篇    下一篇

研究论文

碳氟键均裂解离能的密度泛函理论研究

王华静, 傅尧*, 刘磊, 郭庆祥   

  1. (中国科学技术大学化学系 合肥 230026)
  • 投稿日期:2006-11-09 修回日期:2007-04-21 发布日期:2007-09-28
  • 通讯作者: 傅尧

Density Functional Theory Study on Homolytic Bond Dissociation Enthalpies of Carbon-Fluorine Bond

WANG Hua-Jing; FU Yao*; LIU Lei; GUO Qing-Xiang   

  1. (Department of Chemistry, University of Science and Technology of China, Hefei 230026)
  • Received:2006-11-09 Revised:2007-04-21 Published:2007-09-28
  • Contact: FU Yao

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1107

被引次数

13

运用6种密度泛函方法(B3LYP, B3P86, B3PW91, PBE1PBE, MPW1B95, MPW1K)对15个含氟有机化合物的碳氟键均裂解离能进行理论计算, 得到的理论值与实验值比较, 发现B3P86方法用于碳氟键均裂解离能的计算相对可靠. 使用验证后的理论方法对含氟杂环有机化合物和卤氟烃中的碳氟键均裂解离能进行了预测和分析, 并进一步讨论了α-取代基效应以及Hammett型取代基效应对碳氟键均裂解离能的影响.

关键词: 密度泛函, 键均裂解离能, 杂环化合物, 卤氟烃

Six density functional methods (B3LYP, B3P86, B3PW91, PBE1PBE, MPW1B95, MPW1K) were employed to calculate C—F homolytic bond dissociation enthalpies (BDEs) of 15 fluorine containing organic compounds. Theoretical BDEs were compared with the available experimental values to confirm the suitability of these methods. It was found that B3P86 method has a comparable reliable performance. The BDEs of fluorine containing heterocycles and fluorochlorohydrocarbons were computed by carefully benchmarked method. In addition, the α-substituent effect and Hammett relationship were discussed.

Key words: density functional theory, bond dissociation enthalpy, heterocycle, fluorochlorohydrocarbon