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Kinetic insights into ethynyl radical with isobutane and neopentane

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Abstract

The rate constants of ethynyl (C2H) radical reaction with isobutane (kiso) and neopentane (kneo) were calculated for the first time using canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) in the temperature range of 150–5000 K. The geometries and frequencies of all the stationary points were calculated at the M06-2X/Aug-cc-pVTZ level of theory. Thermodynamics (ΔH°298 and ΔG°298) results govern that the title reactions are highly exothermic and spontaneous in nature. The rate constants obtained over the temperature range of 150–300 K were used to derive the modified Arrhenius expressions: kiso = 6.84 × 10–19 T2.5 exp[1496/T] and kneo = 1.72 × 10–17 T2.0 exp[938/T] cm3 molecule−1 s−1. Branching ratio calculation for the reaction of C2H radical with isobutane shows that the tertiary-H abstraction channel is dominant (> 95%) over the complete temperature range.

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Acknowledgements

The authors thank Professor Donald G. Truhlar and his group for providing the POLYRATE 2008 and GAUSSRATE 2009A programs.

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Authors and Affiliations

  1. Department of Chemistry, National Institute of Technology, Raipur, 492010, India

    Manas Ranjan Dash

  2. Department of Chemistry, National Taiwan University, Taipei, 10617, Taiwan

    Balaganesh Muthiah & King-Chuen Lin

  3. Department of Environmental Sciences, Sambalpur University, Sambalpur, 768019, India

    Subhashree Subhadarsini Mishra

  4. Chemistry Research Centre, National Engineering College, Kovilpatti, Tamilnadu, India

    Balakumaran Annaraj

  5. Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, 10617, Taiwan

    King-Chuen Lin

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  1. Manas Ranjan Dash
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Dash, M.R., Muthiah, B., Mishra, S.S. et al. Kinetic insights into ethynyl radical with isobutane and neopentane. Theor Chem Acc 140, 134 (2021). https://doi.org/10.1007/s00214-021-02833-x

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