Theoretical Studies on Mechanism and Kinetics of the Hydrogen-Abstraction Reaction of CF 3 CH 2 CHO with OH Radicals

The hydrogen abstraction reaction of $CF_3CH_2CHO$ + OH has been studied theoretically by dual-level direct dynamics method. Two stable conformers, trans- and cis-$CF_3CH_2CHO$, have been located, and there are four distinct OH hydrogen-abstraction channels from t-$CF_3CH_2CHO$ and two channels from...

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Published inBulletin of the Korean Chemical Society Vol. 32; no. 4; pp. 1187 - 1194
Main Authors Ci, Cheng-Gang, Yu, Hong-Bo, Wan, Su-Qin, Liu, Jing-Yao, Sun, Chia-Chung
Format Journal Article
LanguageKorean
Published 2011
Subjects
Reaction mechanism
Density functional theory
Direct dynamics method
Rate constant
Variational transition-state theory
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Summary:The hydrogen abstraction reaction of $CF_3CH_2CHO$ + OH has been studied theoretically by dual-level direct dynamics method. Two stable conformers, trans- and cis-$CF_3CH_2CHO$, have been located, and there are four distinct OH hydrogen-abstraction channels from t-$CF_3CH_2CHO$ and two channels from c-$CF_3CH_2CHO$. The required potential energy surface information for the kinetic calculation was obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants, which were calculated using improved canonical transitionstate theory with small-curvature tunneling correction (ICVT/SCT) were fitted by a four-parameter Arrhenius equation. It is shown that the reaction proceeds predominantly via the H-abstraction from the -CHO group over the temperature range 200-2000 K. The calculated rate constants were in good agreement with the experimental data between 263 and 358 K.
Bibliography:KISTI1.1003/JNL.JAKO201115037886529
ISSN:0253-2964
1229-5949