Dual-level direct dynamics studies on the hydrogen abstraction reactions of fluorine atoms with CF3CH2X(X=F,Cl) |
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Authors: | Li Wang Yuan Zhao Jing Zhang Yanna Dai Jinglai Zhang |
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Affiliation: | (1) Institute of Environmental and Analytical Sciences, Institute of Fine Chemistry and Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004, People’s Republic of China; |
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Abstract: | The kinetic properties of the hydrogen abstraction reactions of CF3CH2F + F → CF3CHF + HF (R1) and CF3CH2Cl + F → CF3CHCl + HF (R2) have been studied by dual-level direct dynamics method. Optimized geometries and frequencies of all the stationary points and extra points along the minimum-energy path (MEP) were obtained at the B3LYP/6-311 + G(2d,2p) level. Two complexes with energies less than that of the reactants were located in the reactant side of each reaction. The energy profiles were further refined with the interpolated single-point energies (ISPE) method at the G3(MP2) level of theory. Using canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT) method, the rate constants were evaluated over a wide temperature range of 200–2,000 K. Our calculations have shown that C–H bond activity decreases when one hydrogen atom of CF3CH3 is substituted by a fluorine atom, than when substituted with a chlorine atom. This is in good agreement with the experimental results. |
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