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Quantum and quasiclassical calculations on the OH+CO[r arrow]CO[sub 2]+H reaction

Journal Article · · Journal of Chemical Physics; (United States)
DOI:https://doi.org/10.1063/1.466057· OSTI ID:6299294
 [1];  [2]
  1. Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom)
  2. Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113 (United States)

Scattering calculations on the OH+CO[r arrow]CO[sub 2]+H reaction are reported using both quantum and quasiclassical methods. The rotating bond approximation is used in the quantum calculations. This method explicitly treats the OH vibration and CO rotation in the reactants and the bending vibration and a local CO stretch in the CO[sub 2] product. Analogous quasiclassical trajectory computations are also reported. A potential energy surface obtained as a fit to [ital ab] [ital initio] data is used. The quantum reaction probabilities are dominated by sharp resonances corresponding to vibrationally excited states of the HOCO complex formed in the reaction. The quantum and quasiclassical lifetimes of these resonances compare quite well with measurements made by Wittig [ital et] [ital al]. Calculations of differential cross sections, rate coefficients, and CO[sub 2] vibrational product distributions are also compared with experimental data. The comparisons of quantum and quasiclassical calculations for models that treat explicitly different numbers of degrees of freedom provide detailed insight into the dynamics of the OH+CO reaction.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
6299294
Journal Information:
Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 99:6; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English