Quantumhyphen;mechanical isomerization of a rotationally and vibrationally excited triatomic model molecule

摘要

The effects of rotational excitation on the isomerization dynamics of a model triatomic molecule are analyzed via a quantumhyphen;mechanical analysis. The model is chosen to represent approximately hydrogen cyanide undergoing a 1,2 hydrogen shift isomerization. A new method is developed which combines elements of the discrete variable representationndash;distributed Gaussian basishyphen;function method with a set of parameterhyphen;dependent zerothhyphen;order basis functions. Our results indicate that molecular rotation has a significant effect on unimolecular reaction probability, particularly when changes in the rotational quantum number produce or eliminate critical Fermi resonance interactions.