Direct dynamics studies on hydrogen abstraction reactions of CH3CHFCH3 and CH3CH2CH2F with OH radicals.
The hydrogen abstraction reactions of CH3CHFCH3 and CH3CH2CH2F with the OH radicals have been studied theoretically by a dual-level direct dynamics method. The geometries and frequencies of all the stationary points are optimized by means of the DFT calculation. There are complexes at the reactant side or exit route, indicating these reactions may proceed via indirect mechanisms. To improve the reaction enthalpy and potential barrier of each reaction channel, the single point energy calculation is performed by the MC-QCISD/3 method. The rate constants are evaluated by canonical variational transition state theory (CVT) with the small-curvature tunneling correction method (SCT) over a wide temperature range 200-2000 K. The canculated CVT/SCT rate constants are consistent with available experimental data. The results show that both the variation effect and the SCT contribution play an important role in the calculation of the rate constants. For reactions CH3CHFCH3 and CH3CH2CH2F with OH radicals, the channels of H-abstraction from -CHF- and -CH2- groups are the major reaction channels, respectively, at lower temperature. Furthermore, to further reveal the thermodynamics properties, the enthalpies of formation of reactants CH3CHFCH3, CH3CH2CH2F, and the product radicals CH3CFCH3, CH3CHFCH2, CH3CH2CHF, CH3CHCH2F, and CH2CH2CH2F are studied using isodesmic reactions.
Wang
Ying
Y
Institute of Theoretical Chemistry, State Key Laboratory of Theoetical and Computational Chemistry, Jilin University, Changchun 130023, People's Republic of China.
Liu
Jing-Yao
JY
Yang
Lei
L
Zhao
Xiao-Lei
XL
Ji
Yue-Meng
YM
Li
Ze-Sheng
ZS