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Korean Chemical Society (대한화학회)
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Theoretical Studies on Mechanism and Kinetics of the Hydrogen-Abstraction Reaction of CF3CH2CHO with OH Radicals

  • Ci, Cheng-Gang (State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University) ;
  • Yu, Hong-Bo (State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University) ;
  • Wan, Su-Qin (State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University) ;
  • Liu, Jing-Yao (State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University) ;
  • Sun, Chia-Chung (State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University)
  • Received : 2010.10.05
  • Accepted : 2011.02.02
  • Published : 2011.04.20
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Abstract

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.

Keywords

References

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