A reinterpretation of the mechanism of the simplest reaction at an sp 3-hybridized carbon atom: H + CD4 → CD3 + HD

Jon P. Camden, Hans A. Bechtel, Davida J.Ankeny Brown, Marion R. Martin, Richard N. Zare, Wenfang Hu, György Lendvay, Diego Troya, George C. Schatz

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53 Citations (Scopus)

Abstract

A comparison between theory and experiment for the benchmark H + CD4 → HD + CD3 abstraction reaction yields a reinterpretation of the reaction mechanism and highlights the unexpected contribution of a stripping mechanism. Whereas the best analytic surface fails to reproduce experiment, a first-principles direct-dynamics (on the fly) treatment is in good agreement, showing that the H + CD4 reaction exhibits extreme sensitivity to modest differences in the potential energy surface. We find that bent H-D-C transition state geometries play an important role in the dynamics. A simple model that relates the scattering angle impact parameter and cone of acceptance accounts well for the overall reaction dynamics.

Original languageEnglish
Pages (from-to)11898-11899
Number of pages2
JournalJournal of the American Chemical Society
Volume127
Issue number34
DOIs
Publication statusPublished - Aug 31 2005

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Camden, J. P., Bechtel, H. A., Brown, D. J. A., Martin, M. R., Zare, R. N., Hu, W., Lendvay, G., Troya, D., & Schatz, G. C. (2005). A reinterpretation of the mechanism of the simplest reaction at an sp 3-hybridized carbon atom: H + CD4 → CD3 + HD. Journal of the American Chemical Society, 127(34), 11898-11899. https://doi.org/10.1021/ja052684m