title: A reinterpretation of the mechanism of the simplest reaction at an sp3-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.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
authors.forename: Jon P
authors.initials: JP
authors.lastname: Camden
authors.forename: Hans A
authors.initials: HA
authors.lastname: Bechtel
authors.forename: Davida J
authors.initials: DJ
authors.lastname: Ankeny Brown
authors.forename: Marion R
authors.initials: MR
authors.lastname: Martin
authors.forename: Richard N
authors.initials: RN
authors.lastname: Zare
authors.forename: Wenfang
authors.initials: W
authors.lastname: Hu
authors.forename: György
authors.initials: G
authors.lastname: Lendvay
authors.forename: Diego
authors.initials: D
authors.lastname: Troya
authors.forename: George C
authors.initials: GC
authors.lastname: Schatz