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A quasiclassical trajectory study of the reaction OH + CO {r_arrow} H + CO{sub 2}.

Journal Article · · J. Chem. Phys.
DOI:https://doi.org/10.1063/1.1602061· OSTI ID:961292

A new, full-dimensional potential energy surface has been constructed to describe the OH+CO{leftrightarrow}H+CO{sub 2} reactive system. The new surface modifies the existing many body expansion potential of Bradley and Schatz based on recent ab initio calculations and incorporates an entirely new hybrid surface to accurately describe the OH+CO entrance channel and two possible van der Waals complexes, OH-CO and OH-OC. Quasiclassical trajectory calculations have been performed for the reaction OH+CO{yields}H+CO{sub 2} using the new surface in order to examine the impact of the changes in the surface, to evaluate the accuracy of the surface by comparing to experimental results, and to investigate the reaction dynamics of this interesting complex-forming system. It is shown that the improvement in the description of the entrance channel has a rather large effect on overall reactivity and response to reagent rotational and vibrational excitation, but has little effect on various product properties such as angular and translational energy distributions, which still compare well to experiment. Also, although the reaction forms the intermediate complex HOCO, it is shown that energy is not completely equilibrated among all internal modes and, as a result, there is a strong correlation between reagent and product excitation.

Research Organization:
Argonne National Laboratory (ANL)
Sponsoring Organization:
SC; NSF
DOE Contract Number:
AC02-06CH11357
OSTI ID:
961292
Report Number(s):
ANL/CHM/JA-46274
Journal Information:
J. Chem. Phys., Journal Name: J. Chem. Phys. Journal Issue: 12 ; Sep. 22, 2003 Vol. 119; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
ENGLISH

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