Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

A quasiclassical trajectory study of the OH+CO reaction

Journal Article · · Journal of Chemical Physics; (USA)
DOI:https://doi.org/10.1063/1.461076· OSTI ID:5552702
;  [1];  [2]
  1. Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113 (US)
  2. Theoretical Chemistry Group, Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (US)

We present a quasiclassical trajectory study of the OH+CO reaction using a potential surface that has been derived from {ital ab} {ital initio} calculations. Among quantities that have been studied are cross sections for reaction and for HOCO complex formation, cross sections associated with reaction from excited vibrational and rotational states, product energy partitioning and CO{sub 2} vibrational-state distributions, HOCO lifetime distributions, and thermal and state-resolved rate constants. We also present the results of Rice--Ramsberger--Kassel--Marcus (RRKM) calculations, using the same potential-energy surface, of HOCO lifetimes and of reactive and complex formation rate constants. The trajectory results indicate that the dominant mechanism for reaction involves complex formation at low energies. However, a direct reaction mechanism is responsible for half the reactive cross section at higher energies. This leads to a rate constant that is weakly temperature dependent at low temperatures, and becomes strongly temperature dependent at high temperature. Our trajectory results agree with measured rates over a wide range of temperatures, but the trajectory results at low temperatures are dominated by classical leak'' through zero-point barriers, so this agreement may be somewhat fortuitous.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL
OSTI ID:
5552702
Journal Information:
Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 95:3; ISSN JCPSA; ISSN 0021-9606
Country of Publication:
United States
Language:
English