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

Abstract

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 CF 3CCl CH 2 and cis-CF 3CH CHCl were calculated to be 2.39 × 10 −12 and 5.10 × 10 −13 cm 3 molecule −1 s −1, which suggests that the atmospheric lifetimes of CF 3CCl CH 2 and cis-CF 3CH CHCl are approximately 5 and 23 days, respectively.