A reinterpretation of the mechanism of the simplest reaction at an sp3-hybridized carbon atom: H + CD4 --> CD3 + HD.
J Am Chem Soc
; 127(34): 11898-9, 2005 Aug 31.
Article
em En
| MEDLINE
| ID: mdl-16117502
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.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2005
Tipo de documento:
Article
País de afiliação:
Estados Unidos