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

Andrew E Pomerantz; Jon P Camden; Albert S Chiou; Florian Ausfelder; Navdeep Chawla; William L Hase; Richard N Zare

doi:10.1021/ja055440a

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

J Am Chem Soc. 2005 Nov 30;127(47):16368-9. doi: 10.1021/ja055440a.

Authors

Andrew E Pomerantz¹, Jon P Camden, Albert S Chiou, Florian Ausfelder, Navdeep Chawla, William L Hase, Richard N Zare

Affiliation

¹ Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.

PMID: 16305203
DOI: 10.1021/ja055440a

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.