Mechanistic study and kinetic properties of the CF3CHO + Cl reaction

作者：Gao Hong; Wang Ying; Wang Qin; Liu JingYao^*

来源：Science China Chemistry, 2012, 55(10): 2197-2201.

DOI：10.1007/s11426-012-4745-0

• direct dynamics
• rate constant
• variational transition-state theory

Theoretical investigations have been carried out on the mechanism and kinetics for the reaction of CF3CHO + Cl using duallevel direct dynamics method. The potential energy surface information was obtained at the MC-QCISD/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.

• 出版日期2012-10
• 单位吉林大学