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Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms |
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| Authors: | Hui Zhang Gui-ling Zhang Jing-yao Liu Wen-jie Hou Bo Liu Ze-sheng Li |
| Institution: | 1. College of Chemical and Environmental Engineering, Harbin University of Science and Technology, 150080, Harbin, People’s Republic of China 2. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, 130023, Changchun, People’s Republic of China 3. Department of Chemistry, Harbin Institute of Technology, Academy of Fundamental and Interdisciplinary Sciences, 150080, Harbin, People’s Republic of China |
| Abstract: | The multiple-channel reactions Cl + Si(CH3)4 and Br + Si(CH3)4 are investigated by direct dynamics method. The minimum energy path is calculated 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 individual reaction channel are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200–3,000 K. The theoretical three-parameter expression k 1(T) = 9.97 × 10?13 T 0.54exp(613.22/T) and k 2(T) = 1.16 × 10?17 T 2.30exp(?3525.88/T) (in unit of cm3 molecule?1 s?1) are given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smaller barrier height among feasible channels considered. |
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