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

Research output: Contribution to journalArticle

49 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

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Benchmarking
Dilatation and Curettage
Diptera
Carbon
Atoms
Potential energy surfaces
Cones
Experiments
Scattering
Geometry

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

A reinterpretation of the mechanism of the simplest reaction at an sp 3-hybridized carbon atom : H + CD4 → CD3 + HD. / Camden, Jon P.; Bechtel, Hans A.; Brown, Davida J Ankeny; Martin, Marion R.; Zare, Richard N.; Hu, Wenfang; Lendvay, György; Troya, Diego; Schatz, George C.

In: Journal of the American Chemical Society, Vol. 127, No. 34, 31.08.2005, p. 11898-11899.

Research output: Contribution to journalArticle

Camden, Jon P. ; Bechtel, Hans A. ; Brown, Davida J Ankeny ; Martin, Marion R. ; Zare, Richard N. ; Hu, Wenfang ; Lendvay, György ; Troya, Diego ; Schatz, George C. / A reinterpretation of the mechanism of the simplest reaction at an sp 3-hybridized carbon atom : H + CD4 → CD3 + HD. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 34. pp. 11898-11899.
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