A reinterpretation of the mechanism of the simplest reaction at an sp3-hybridized carbon atom: H + CD4 --> CD3 + HD.
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.
Camden
Jon P
JP
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
Bechtel
Hans A
HA
Ankeny Brown
Davida J
DJ
Martin
Marion R
MR
Zare
Richard N
RN
Hu
Wenfang
W
Lendvay
György
G
Troya
Diego
D
Schatz
George C
GC