• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3718-3722
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• 2010

Theoretical investigations are carried out on the title reaction by means of ab-initio and DFT methods. The optimized geometries, frequencies and minimum energy path are obtained at UB3LYP/6-311G(d,p) level. Single point energy calculations are performed at MP2 and MP4 levels of theory. Energetics are further refined by calculating the energy of the species with a modified Gaussian-2 method, G2M(CC,MP2). The rate constant of the reaction is calculated using Canonical Transition State Theory (CTST) utilizing the ab-initio data obtained during the present study and is found to be $5.47{\times}10^{-12}\;cm^3\;molecule^{-1}s^{-1}$ at 298 K and 1 atm.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1187-1194
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• 2011

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.

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1385-1390
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• 2014

Hydrofluoroethers (HFEs) are developed as a suitable for the replacement of environmentally hazardous CFCs and are termed as third generation refrigerants. One of the major products of decomposition of HFEs in the atmosphere is a fluoroester. The present study relates to the OH and Cl initiated oxidation of $CF_3C(O)OCH_2CF_3$ formed from the oxidation of HFE-356mff. The latter is used as a solvent in the industry and reaches the atmosphere without any degradation. Kinetics of the titled molecule has been studied at MPWB1K/6-31+G(d,p) level of theory. Single point energy calculations have been made at G2(MP2) level of theory and barrier heights are determined. The rate constants are calculated using canonical transition state theory. Tunnelling correction are made using one-dimensional Eckart potential barrier. The rate constant calculated during the present study are compared with the experimental values determined using relative rate method and FTIR detection technique.