title: Mode specificity and product energy disposal in unimolecular reactions: insights from the sudden vector projection model.
abstract: A simple model is proposed to predict mode specificity and product energy disposal in unimolecular dissociation reactions. This so-called Sudden Vector Projection (SVP) model quantifies the coupling of a reactant or product mode with the reaction coordinate at the transition state by projecting the corresponding normal mode vector onto the imaginary frequency mode at the saddle point. Due to the sudden assumption, SVP predictions for mode specificity are expected to be valid only when the reactant molecule has weak intermodal coupling. On the other hand, the sudden limit is generally satisfied for its predictions of product energy disposal in unimolecular reactions with a tight barrier. The SVP model is applied to several prototypical systems and the agreement with available experimental and theoretical results is satisfactory.
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Jun
authors.initials: J
authors.lastname: Li
authors.forename: Hua
authors.initials: H
authors.lastname: Guo
mesh_terms: D011789:Quantum Theory