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.
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.
Pomerantz
Andrew E
AE
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
Camden
Jon P
JP
Chiou
Albert S
AS
Ausfelder
Florian
F
Chawla
Navdeep
N
Hase
William L
WL
Zare
Richard N
RN