An ab initio dynamics study on the reaction of O(P-3) with CH3CH-CH2 ((1)A ')

作者：Zhang Weichao^*; Du Benni; Feng Changjun

来源：Journal of Molecular Structure (Theochem), 2007, 806(1-3): 121-129.

DOI：10.1016/j.theochem.2006.11.014

• propene
• QCISD(T)
• reaction mechanism
• rate constants

The reaction of O(P-3) with propene on the triplet potential energy surface is investigated using the unrestricted second-order Moller-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(P-3) 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.

• 出版日期2007-3-31
• 单位江苏师范大学