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Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms

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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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Acknowledgments

The authors thank Professor Donald G. Truhlar for providing POLYRATE 9.1 program. This work is supported by the National Natural Science Foundation of China (20333050, 20303007, 50743013, and 20973049), the Program for New Century Excellent Talents in University (NCET), the Key subject of Science and Technology by the Ministry of Education of China, the Key subject of Science and Technology by Jilin Province, the Foundation for University Key Teacher by the Department of Education of Heilongjiang Province (1152G010), the SF of Graduate Innovation by Department of Education of Heilongjiang province (YJSCX2009-055HLJ), the SF for Postdoctoral of HLJ province (LBH-Q07058), and Natural Science Foundation of Heilongjiang Province (B200605).

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Authors and Affiliations

  1. College of Chemical and Environmental Engineering, Harbin University of Science and Technology, 150080, Harbin, People’s Republic of China

    Hui Zhang, Gui-ling Zhang, Wen-jie Hou & Bo Liu

  2. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, 130023, Changchun, People’s Republic of China

    Jing-yao Liu

  3. Department of Chemistry, Harbin Institute of Technology, Academy of Fundamental and Interdisciplinary Sciences, 150080, Harbin, People’s Republic of China

    Ze-sheng Li

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  1. Hui Zhang
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Correspondence to Bo Liu.

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Zhang, H., Zhang, Gl., Liu, Jy. et al. Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms. Theor Chem Acc 125, 75–82 (2010). https://doi.org/10.1007/s00214-009-0664-3

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