An ab initio dynamics study on the reaction of O(3P) with CH3CHCH2 (1A′)

The reaction of O(3P) with propene on the triplet potential energy surface is investigated using the unrestricted second-order Møller-Plesset perturbation (UMP2) and QCISD(T)/6-311++G(3df,2p) level methods. The calculational results indicate that the initial step of the reaction consists of an attachment of the electrophilic O(3P) atom to both the carbon atoms of the double bond to form lower-energy intermediates IM1 and IM2. Among all these reaction channels the formation of CH2C(O)H+CH3 from IM2 is the dominant one and the products of CH3COCH2+H from IM2 and CH3CHC(O)H+H from IM1 are the secondary ones. The conventional transition state calculations are carried out with Wigner's tunneling correction at 298-500 K. The rate constants and activation energy calculated at the QCISD(T)/6-311++G(3df,2p) level within the range of temperature 298-500 K are in good agreement with the experimental values.