Theoretical Study of CH3CH=CH2+O(D-1) Reaction: Mechanism and Kinetics

The mechanism and kinetics for the reaction of propene(CH3CH=CH2) molecule with O(D-1) atom were investigated theoretically. The electronic structure information of the potential energy surface(PES) was obtained at the B3LYP/6-311+G(d,p) level, and the single-point energies were refined by the multi-level MCG3-MPWB method. The calculated results show that O(D-1) atom can attack CH3CH=CH2 via the barrierless insertion mechanism to form four energy-riched intermediates CH3C(OH)CH2(IM1), CH3CHCHOH(IM2), CH2OHCHCH2(IM3) and cyclo-CH2OCHCH3(IM4), respectively, on the singlet PES. The branching ratios as well as the pressure- and temperature-dependence of various product channels for this multi-well reaction were predicted by variational transition-state and Rice-Ramsperger-Kassel-Marcus(RRKM) theories. The present results will be useful to gain a deep insight into the reaction mechanism and kinetics of CH3CH=CH2+O(D-1) reaction.