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Theoretical study and rate constant calculations for the reactions of SiHX3 with CF3 and CH3 radicals (X = F, Cl)

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Abstract

Theoretical investigations were carried out on the multi-channel reactions CF3 + SiHF3, CF3 + SiHCl3, CH3 + SiHF3, and CH3 + SiHCl3. Electronic structures were calculated at the MP2/6-311+G(d,p) level, and energetic information further refined by the MC-QCISD (single-point) method. The rate constants for major reaction channels were calculated by the canonical variational transition state theory with small-curvature tunneling correction over the temperature range of 200–1,500 K. The theoretical rate constants were in good agreement with the available experimental data and were fitted to the three parameter expression: k 1a(T) = 2.93 × 10−26 T 4.25 exp (−318.68/T), and k 2a(T) = 3.67 × 10−22 T 2.72 exp (−1,414.22/T), k 3a (T) = 7.00 × 10−24 T 3.27 exp (−384.04/T), k 4a(T) = 6.35 × 10−22 T 2.59 exp (−603.18/T) (in unit of cm3molecule−1s−1) are given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smaller barrier height among four channels considered.

Theoretical investigations on the reaction mechanisms of SiHX3 with CF3 and CH3 radicals. Rate constants were calculated in the temperature range 200―1,500 K. Our calculations indicate that hydrogen abstraction is the major channel, and is important in a wide variety of materials synthesis processes, in glow discharge deposition of amorphous silicon films, and in the semiconductor manufacturing process

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Acknowledgments

The authors thank Professor Donald G. Truhlar for providing the POLYRATE 9.7 program. This work was supported by the National Natural Science Foundation of China (20973077 and 20973049), the Program for New Century Excellent Talents in University (NCET), the Doctoral Fund of Ministry of Education of China (20112303110005), the Foundation for the Department of Education of Heilongjiang Province (1152G010, 11551077), the Key Subject of Science and Technology by the Ministry of Education of China, the SF for leading experts in academe of Harbin of China (2011RFJGS026), the Science Foundation for Distinguished Young Scholar of Heilongjiang Province (JC201206).

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Authors and Affiliations

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

    Hui Zhang & Ping Liu

  2. Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, People’s Republic of China

    Jing-Yao Liu

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

    Ze-Sheng Li

  4. Key Laboratory of Cluster Science of Ministry of Education and School of Chemistry, Beijing Institute of Technology, Beijing, 100081, People’s Republic of China

    Ze-Sheng Li

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  1. Hui Zhang
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Correspondence to Hui Zhang or Ze-Sheng Li.

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Zhang, H., Liu, P., Liu, JY. et al. Theoretical study and rate constant calculations for the reactions of SiHX3 with CF3 and CH3 radicals (X = F, Cl). J Mol Model 19, 1515–1525 (2013). https://doi.org/10.1007/s00894-012-1704-9

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