Mechanistic study and kinetic properties of the CF_3CHO+Cl reaction  

作　　者：GAO Hong WANG Ying WANG Qin LIU JingYao 

机构地区：[1]State Key Laboratory of Theoretical and Computational Chemistry,Institute of Theoretical Chemistry,Jilin University,Changchun 130023,China

出　　处：《Science China Chemistry》2012年第10期2197-2201,共5页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (20973077, 20303007);the Program for New Century Excellent Talents in University (NCET)

摘　　要：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.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.

关 键 词：direct dynamics rate constant variational transition-state theory 

分 类 号：O621.2[理学—有机化学]