A theoretical study of the kinetics of OH radical addition to halogen substituted propenes

The kinetics of the addition of OH radical to propene and a series of halogen substituted propenes have been investigated using DFT, MP2 and CCSD(T) methods. Activation energies based on MP2/cc-pVTZ single point energy calculations on BH&HLYP/cc-pVTZ optimized structures were found to give rate constants in good agreement with experimental values. Using standard transition state theory the rate constants of the OH radical addition to CF3CClCH2 and cis-CF3CHCHCl were calculated to be 2.39 × 10−12 and 5.10 × 10−13 cm3 molecule−1 s−1, which suggests that the atmospheric lifetimes of CF3CClCH2 and cis-CF3CHCHCl are approximately 5 and 23 days, respectively.