Direct ab initio dynamics calculations on the rate constants for the hydrogen-abstraction reaction of C2H5F with O (3P) |
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Authors: | Jing-yao Liu Ze-sheng Li Zhen-wen Dai Xu-ri Huang Chia-chung Sun |
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Institution: | (1) Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, China, CN;(2) Department of Physics, Jilin University, Changchun 130023, China, CN |
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Abstract: | The hydrogen-abstraction reaction C2H5F+O → C2H4F+OH has been studied by a dual-level direct dynamics method. For the reaction, three reaction channels, one for α-abstraction
and two for β-abstraction, have been identified. The potential-energy surface information is obtained at the MP2(full)/6-311G(d,p)
and PMP2(full)/6-311G(3df,3pd) (single-point) levels. By canonical variational transition-state theory, rate constants for
each reaction channel are calculated with a small-curvature tunneling correction. The total rate constant is calculated from
the sum of the individual rate constants and the temperature dependence of the branching ratios is obtained over a wide range
of temperatures from 300 to 5,000 K. The agreement of the rate constants with experiment is good in the experimental temperature
range from 1,000 to 1,250 K. The calculated results indicate that at low temperatures α-abstraction is most likely to be the
major reaction channel, while β-abstraction channels will significantly contribute to the whole reaction rate as the temperature
increases.
Received: 23 January 2002 / Accepted: 23 June 2002 / Published online: 20 September 2002 |
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Keywords: | : Hydrogen abstraction – Direct dynamics – Ab initio – Rate constant – Variational transition state |
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