Direct dynamics study on hydrogen abstraction reaction of CF3CF2CH2OH with OH radical.
The dual-level direct dynamics method has been employed to investigate the H-abstraction reaction of CF(3)CF(2)CH(2)OH with OH radical, which is predicted to have two classes of possible reaction channels caused by different positions of hydrogen atom attack. The minimum-energy path is calculated at the B3LYP/6-311G(d,p) level, and the energetic information is further refined by the MC-QCISD method. To compare the structures, the other method MPW1K/6-311G(d,p) is also applied to this system. Hydrogen-bonded complexes are presented in the reactant and product sides of the three channels, indicating that each reaction may proceed via an indirect mechanism. The rate constants for each reaction channel are evaluated by canonical variational transition-state theory (CVT) with the small-curvature tunneling correction (SCT) over a wide range of temperatures from 200 to 2000 K. The calculated CVT/SCT rate constants are found to be in good agreement with the available experimental values. The result shows that the variational effect is small, and in the lower-temperature range, the SCT effect is important for each reaction. It is shown that hydrogen abstracted from the -CH(2)- position is the major channel, while H-abstraction from the -OH position may be neglected with the temperature increasing.
Wang
Ying
Y
Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun, People's Republic of China.
Liu
Jing-Yao
JY
Li
Ze-Sheng
ZS
Wang
Li
L
Wu
Jia-Yan
JY
Sun
Chia-Chung
CC