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Association reaction between SiH3 and H2O2: a computational study of the reaction mechanism and kinetics

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Abstract

The association reaction between silyl radical (SiH3) and H2O2 has been studied in detail using high-level composite ab initio CBS-QB3 and G4MP2 methods. The global hybrid meta-GGA M06 and M06-2X density functionals in conjunction with 6-311++G(d,p) basis set have also been applied. To understand the kinetics, variational transition-state theory calculation is performed on the first association step, and successive unimolecular reactions are subjected to Rice–Ramsperger–Kassel–Marcus calculations to predict the reaction rate constants and product branching ratios. The bimolecular rate constant for SiH3–H2O2 association in the temperature range 250–600 K, k(T) = 6.89 × 10−13 T −0.163exp(−0.22/RT) cm3 molecule−1 s−1 agrees well with the current literature. The OH production channel, which was experimentally found to be a minor one, is confirmed by the rate constants and branching ratios. Also, the correlation between our theoretical work and experimental literature is established. The production of SiO via secondary reactions is calculated to be one of the major reaction channels from highly stabilized adducts. The H-loss pathway, i.e., SiH2(OH)2 + H, is the major decomposition channel followed by secondary dissociation leading to SiO.

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Acknowledgments

K.S. is very much grateful to the Council of Scientific and Industrial Research (CSIR), Government of India, for providing him research fellowships. A.K.D. is grateful to the Council of Scientific and Industrial Research (CSIR), Govt. of India, for a research grant under scheme number: 03(1168)/10/EMR-II. Thanks are due to Mr. Debasish Mandal for his assistance and helpful discussions. We are thankful to Prof. Vladimir Mokrushin for helping us on time-dependent RRKM master equation simulation with ChemRate.

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Authors and Affiliations

  1. Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata, 700032, India

    Kaushik Sen, Srimanta Pakhira, Chandan Sahu, Deepanwita Ghosh & Abhijit K. Das

  2. Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK

    Bhaskar Mondal

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  1. Kaushik Sen
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Sen, K., Mondal, B., Pakhira, S. et al. Association reaction between SiH3 and H2O2: a computational study of the reaction mechanism and kinetics. Theor Chem Acc 132, 1375 (2013). https://doi.org/10.1007/s00214-013-1375-3

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