A quasiclassical trajectory study of OH rotational excitation in OH+CO collisions using ab initio potential surfaces

Kathleen Kudla, Antonios G. Koures, Lawrence B. Harding, George C Schatz

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

We have performed large basis set configuration interaction calculations to characterize the two potential surfaces (2A′ and 2A″) which correlate to the ground state of OH + CO. Only planar geometries of the four atoms are considered, and the calculations restrict the OH and CO bond distances to their isolated diatomic values. Global representations of these potential surfaces have been developed and used in quasiclassical trajectory studies of rotational excitation in low energy (1-6 kcal/mol) collisions of OH and CO in their respective rovibrational ground states. We find that the collisional excitation cross sections are about equal for the two surfaces, and there is a monotonic increase in each cross section with translational energy. For OH rotational quantum numbers N between 2 and 6 there is approximately a factor of 2-3 decrease in the cross section for each unit increase in N. The energy and N dependence of these cross sections are generally in excellent agreement with recent experiments. We have also explored the sensitivity of these cross sections to the nature of the potential energy surface, and we have used a surface that describes the formation of the intermediate complex HOCO to determine sensitivity of the rotationally inelastic cross sections to complex formation. In agreement with the experiments, we find that the low energy, high N cross sections are appreciably perturbed by complex formation.

Original languageEnglish
Pages (from-to)7465-7473
Number of pages9
JournalJournal of Chemical Physics
Volume96
Issue number10
Publication statusPublished - 1992

Fingerprint

Carbon Monoxide
Trajectories
trajectories
Ground state
collisions
cross sections
excitation
Potential energy surfaces
Experiments
Atoms
Geometry
ground state
energy
sensitivity
configuration interaction
quantum numbers
potential energy
geometry
atoms

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

A quasiclassical trajectory study of OH rotational excitation in OH+CO collisions using ab initio potential surfaces. / Kudla, Kathleen; Koures, Antonios G.; Harding, Lawrence B.; Schatz, George C.

In: Journal of Chemical Physics, Vol. 96, No. 10, 1992, p. 7465-7473.

Research output: Contribution to journalArticle

Kudla, Kathleen ; Koures, Antonios G. ; Harding, Lawrence B. ; Schatz, George C. / A quasiclassical trajectory study of OH rotational excitation in OH+CO collisions using ab initio potential surfaces. In: Journal of Chemical Physics. 1992 ; Vol. 96, No. 10. pp. 7465-7473.
@article{a200fd2e45034d43ae994d8d2bffa207,
title = "A quasiclassical trajectory study of OH rotational excitation in OH+CO collisions using ab initio potential surfaces",
abstract = "We have performed large basis set configuration interaction calculations to characterize the two potential surfaces (2A′ and 2A″) which correlate to the ground state of OH + CO. Only planar geometries of the four atoms are considered, and the calculations restrict the OH and CO bond distances to their isolated diatomic values. Global representations of these potential surfaces have been developed and used in quasiclassical trajectory studies of rotational excitation in low energy (1-6 kcal/mol) collisions of OH and CO in their respective rovibrational ground states. We find that the collisional excitation cross sections are about equal for the two surfaces, and there is a monotonic increase in each cross section with translational energy. For OH rotational quantum numbers N between 2 and 6 there is approximately a factor of 2-3 decrease in the cross section for each unit increase in N. The energy and N dependence of these cross sections are generally in excellent agreement with recent experiments. We have also explored the sensitivity of these cross sections to the nature of the potential energy surface, and we have used a surface that describes the formation of the intermediate complex HOCO to determine sensitivity of the rotationally inelastic cross sections to complex formation. In agreement with the experiments, we find that the low energy, high N cross sections are appreciably perturbed by complex formation.",
author = "Kathleen Kudla and Koures, {Antonios G.} and Harding, {Lawrence B.} and Schatz, {George C}",
year = "1992",
language = "English",
volume = "96",
pages = "7465--7473",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "10",

}

TY - JOUR

T1 - A quasiclassical trajectory study of OH rotational excitation in OH+CO collisions using ab initio potential surfaces

AU - Kudla, Kathleen

AU - Koures, Antonios G.

AU - Harding, Lawrence B.

AU - Schatz, George C

PY - 1992

Y1 - 1992

N2 - We have performed large basis set configuration interaction calculations to characterize the two potential surfaces (2A′ and 2A″) which correlate to the ground state of OH + CO. Only planar geometries of the four atoms are considered, and the calculations restrict the OH and CO bond distances to their isolated diatomic values. Global representations of these potential surfaces have been developed and used in quasiclassical trajectory studies of rotational excitation in low energy (1-6 kcal/mol) collisions of OH and CO in their respective rovibrational ground states. We find that the collisional excitation cross sections are about equal for the two surfaces, and there is a monotonic increase in each cross section with translational energy. For OH rotational quantum numbers N between 2 and 6 there is approximately a factor of 2-3 decrease in the cross section for each unit increase in N. The energy and N dependence of these cross sections are generally in excellent agreement with recent experiments. We have also explored the sensitivity of these cross sections to the nature of the potential energy surface, and we have used a surface that describes the formation of the intermediate complex HOCO to determine sensitivity of the rotationally inelastic cross sections to complex formation. In agreement with the experiments, we find that the low energy, high N cross sections are appreciably perturbed by complex formation.

AB - We have performed large basis set configuration interaction calculations to characterize the two potential surfaces (2A′ and 2A″) which correlate to the ground state of OH + CO. Only planar geometries of the four atoms are considered, and the calculations restrict the OH and CO bond distances to their isolated diatomic values. Global representations of these potential surfaces have been developed and used in quasiclassical trajectory studies of rotational excitation in low energy (1-6 kcal/mol) collisions of OH and CO in their respective rovibrational ground states. We find that the collisional excitation cross sections are about equal for the two surfaces, and there is a monotonic increase in each cross section with translational energy. For OH rotational quantum numbers N between 2 and 6 there is approximately a factor of 2-3 decrease in the cross section for each unit increase in N. The energy and N dependence of these cross sections are generally in excellent agreement with recent experiments. We have also explored the sensitivity of these cross sections to the nature of the potential energy surface, and we have used a surface that describes the formation of the intermediate complex HOCO to determine sensitivity of the rotationally inelastic cross sections to complex formation. In agreement with the experiments, we find that the low energy, high N cross sections are appreciably perturbed by complex formation.

UR - http://www.scopus.com/inward/record.url?scp=0000190611&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000190611&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000190611

VL - 96

SP - 7465

EP - 7473

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 10

ER -