Quantum and quasiclassical calculations on the OH+CO→CO2+H reaction

David C. Clary, George C Schatz

Research output: Contribution to journalArticle

101 Citations (Scopus)

Abstract

Scattering calculations on the OH+CO→CO2+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 CO2 product. Analogous quasiclassical trajectory computations are also reported. A potential energy surface obtained as a fit to ab 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 et al. Calculations of differential cross sections, rate coefficients, and CO2 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.

Original languageEnglish
Pages (from-to)4578-4589
Number of pages12
JournalJournal of Chemical Physics
Volume99
Issue number6
Publication statusPublished - 1993

Fingerprint

Carbon Monoxide
Potential energy surfaces
bending vibration
Degrees of freedom (mechanics)
products
Excited states
degrees of freedom
potential energy
Trajectories
trajectories
Scattering
life (durability)
vibration
cross sections
coefficients
approximation
scattering
excitation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Quantum and quasiclassical calculations on the OH+CO→CO2+H reaction. / Clary, David C.; Schatz, George C.

In: Journal of Chemical Physics, Vol. 99, No. 6, 1993, p. 4578-4589.

Research output: Contribution to journalArticle

@article{e2ce8568f4f747ff8f1af029f35c8ab4,
title = "Quantum and quasiclassical calculations on the OH+CO→CO2+H reaction",
abstract = "Scattering calculations on the OH+CO→CO2+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 CO2 product. Analogous quasiclassical trajectory computations are also reported. A potential energy surface obtained as a fit to ab 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 et al. Calculations of differential cross sections, rate coefficients, and CO2 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.",
author = "Clary, {David C.} and Schatz, {George C}",
year = "1993",
language = "English",
volume = "99",
pages = "4578--4589",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "6",

}

TY - JOUR

T1 - Quantum and quasiclassical calculations on the OH+CO→CO2+H reaction

AU - Clary, David C.

AU - Schatz, George C

PY - 1993

Y1 - 1993

N2 - Scattering calculations on the OH+CO→CO2+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 CO2 product. Analogous quasiclassical trajectory computations are also reported. A potential energy surface obtained as a fit to ab 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 et al. Calculations of differential cross sections, rate coefficients, and CO2 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.

AB - Scattering calculations on the OH+CO→CO2+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 CO2 product. Analogous quasiclassical trajectory computations are also reported. A potential energy surface obtained as a fit to ab 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 et al. Calculations of differential cross sections, rate coefficients, and CO2 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.

UR - http://www.scopus.com/inward/record.url?scp=36449003757&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=36449003757&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:36449003757

VL - 99

SP - 4578

EP - 4589

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 6

ER -