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 CF3CCl{double bond, long}CH2 and cis-CF3CH{double bond, long}CHCl 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 CF3CCl{double bond, long}CH2 and cis-CF3CH{double bond, long}CHCl are approximately 5 and 23 days, respectively. © 2009 Elsevier B.V. All rights reserved.