| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1313939 | Journal of Fluorine Chemistry | 2015 | 10 Pages |
•The hydrogen-abstraction mechanism of the CF3C(O)OCH2CH3 + OH reaction was investigated.•Two conformers of CF3C(O)OCH2CH3 were considered in the kinetic calculation.•The individual ICVT/SCT rate constants for each H-abstraction channel were evaluated.
The hydrogen-abstraction reaction of CF3C(O)OCH2CH3 + OH has been studied theoretically by a dual-level direct dynamics method. For the two stable conformers (I, II) of CF3C(O)OCH2CH3, three distinct transition states are identified for the reaction of conformer I (Cs symmetry) + OH (R1), and five transition states are ascertained for the reaction of conformer II (C1 symmetry) + OH (R2). The potential energy surface information for the kinetic calculation is obtained at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. The rate constants for each reaction channel are calculated using improved canonical variational transition-state theory (ICVT) with small-curvature tunneling correction (SCT) and are fitted by a three-parameter Arrhenius equation within 200–1000 K. The calculated rate constant is in reasonable agreement with the experimental data at 298 K.
Graphical abstractSchematic potential energy surfaces for both the CF3C(O)OCH2CH3 (I) + OH and the CF3C(O)OCH2CH3 (II) + OH reactions.Figure optionsDownload full-size imageDownload as PowerPoint slide
