title: Reaction products with internal energy beyond the kinematic limit result from trajectories far from the minimum energy path: an example from H + HBr --> H2 + Br.
abstract: The importance of reactive trajectories straying far from the minimum energy path is demonstrated for the bimolecular reaction H + HBr --> H2(v', j') + Br at 53 kcal/mol collision energy. Product quantum state distributions are measured and calculated using the quasi-classical trajectory technique, and the calculations indicate that highly internally excited H2 products result from indirect reactive trajectories with bent transition states. A general argument is made suggesting that reaction products with internal energy exceeding a kinematic constraint can, in general, be attributed to reactive collisions straying far from the minimum energy path.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
authors.forename: Andrew E
authors.initials: AE
authors.lastname: Pomerantz
authors.forename: Jon P
authors.initials: JP
authors.lastname: Camden
authors.forename: Albert S
authors.initials: AS
authors.lastname: Chiou
authors.forename: Florian
authors.initials: F
authors.lastname: Ausfelder
authors.forename: Navdeep
authors.initials: N
authors.lastname: Chawla
authors.forename: William L
authors.initials: WL
authors.lastname: Hase
authors.forename: Richard N
authors.initials: RN
authors.lastname: Zare