Mechanistic study and kinetic properties of the CF3CHO + Cl reaction |
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Authors: | Hong Gao Ying Wang Qin Wang JingYao Liu |
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Affiliation: | Key Laboratory of Theoretical and Computational Chemistry; Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China |
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Abstract: | Theoretical investigations have been carried out on the mechanism and kinetics for the reaction of CF 3 CHO + Cl using duallevel direct dynamics method. The potential energy surface information was obtained at the MCQCISD/3//MP2/cc-pVDZ level and the kinetic calculations were done using variational transition state theory with interpolated single-point energy (VTST-ISPE) approach. The calculated results show that the reaction proceeds primarily via the H-abstraction channel, while the Cl-addition channel is unfavorable due to the higher barriers. The improved canonical variational transition-state theory (ICVT) with the small-curvature tunneling correction (SCT) was used to calculate the rate constants. The theoretical rate constants at room temperature are in general agreement with the experimental values. A three-parameter rate constant expression was fitted over a wide temperature range of 200–2000 K. |
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Keywords: | direct dynamics rate constant variational transition-state theory |
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