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