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

doi:10.1021/ja052684m

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

59 Scopus citations

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 language	English (US)
Pages (from-to)	11898-11899
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	34
DOIs	https://doi.org/10.1021/ja052684m
State	Published - Aug 31 2005

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja052684m

Cite this

@article{ae4f95ab3c1e4e4b9ba6b17d2c2c58f8,

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

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.",

author = "Camden, {Jon P.} and Bechtel, {Hans A.} and Brown, {Davida J.Ankeny} and Martin, {Marion R.} and Zare, {Richard N.} and Wenfang Hu and Gy{\"o}rgy Lendvay and Diego Troya and Schatz, {George C.}",

year = "2005",

month = aug,

day = "31",

doi = "10.1021/ja052684m",

language = "English (US)",

volume = "127",

pages = "11898--11899",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "34",

}

TY - JOUR

T1 - A reinterpretation of the mechanism of the simplest reaction at an sp 3-hybridized carbon atom

T2 - H + CD4 → CD3 + HD

AU - Camden, Jon P.

AU - Bechtel, Hans A.

AU - Brown, Davida J.Ankeny

AU - Martin, Marion R.

AU - Zare, Richard N.

AU - Hu, Wenfang

AU - Lendvay, György

AU - Troya, Diego

AU - Schatz, George C.

PY - 2005/8/31

Y1 - 2005/8/31

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=24144473116&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=24144473116&partnerID=8YFLogxK

U2 - 10.1021/ja052684m

DO - 10.1021/ja052684m

M3 - Article

C2 - 16117502

AN - SCOPUS:24144473116

SN - 0002-7863

VL - 127

SP - 11898

EP - 11899

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 34

ER -

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

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this