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Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

Author

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  • Zhiqiang Zhao

    (State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences
    University of Chinese Academy of Sciences)

  • Zhaojun Zhang

    (State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Shu Liu

    (State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences)

  • Dong H Zhang

    (State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences
    Center for Advanced Chemical Physics and 2011 Frontier Center for Quantum Science and Technology, University of Science and Technology of China)

Abstract

Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode.

Suggested Citation

  • Zhiqiang Zhao & Zhaojun Zhang & Shu Liu & Dong H Zhang, 2017. "Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism," Nature Communications, Nature, vol. 8(1), pages 1-7, April.
    • Handle: RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_ncomms14506
    DOI: 10.1038/ncomms14506
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