Theoretical studies on the reactions CH3SCH3 with OH,CF3, and CH3 radicals |
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| Authors: | Hui Zhang Gui‐Ling Zhang Jing‐Yao Liu Miao Sun Bo Liu Ze‐Sheng Li |
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| Affiliation: | 1. Department of Chemistry, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, People's Republic of China;2. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, People's Republic of China;3. Academy of Fundamental and Interdisciplinary Sciences, Department of Chemistry, Harbin Institute of Technology, Harbin 150080, People's Republic of China |
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| Abstract: | The multiple‐channel reactions OH + CH3SCH3 → products, CF3 + CH3SCH3 → products, and CH3 + CH3SCH3 → products are investigated by direct dynamics method. The optimized geometries, frequencies, and minimum energy path are all obtained at the MP2/6‐31+G(d,p) level, and energetic information is further refined by the MC‐QCISD (single‐point) method. The rate constants for eight reaction channels are calculated by the improved canonical variational transition state theory with small‐curvature tunneling contribution over the temperature range 200–3000 K. The total rate constants are in good agreement with the available experimental data and the three‐parameter expressions k1 = 4.73 × 10?16T1.89 exp(?662.45/T), k2 = 1.02 × 10?32T6.04 exp(933.36/T), k3 = 3.98 × 10?35T6.60 exp(660.58/T) (in unit of cm3 molecule?1 s?1) over the temperature range of 200–3000 K are given. Our calculations indicate that hydrogen abstraction channels are the major channels and the others are minor channels over the whole temperature range. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 |
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| Keywords: | gas‐phase reaction transition state rate constants |
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