Theoretical study of the H+O3↔OH+O2↔ O+HO2 system

Michel Dupuis, G. Fitzgerald, B. Hammond, W. A. Lester, H. F. Schaefer

Research output: Contribution to journalArticle

80 Citations (Scopus)

Abstract

The key features of the H+O3 potential energy surface have been determined using ab initio quantum mechanical methods. The electronic wave function used is a multiconfiguration Hartree-Fock wave function which provides a qualitatively correct description of various reactive channels. It is found that the H+O3→HO+O2 reaction proceeds along a nonplanar pathway in which the H atom descends vertically to the plane containing the ozone molecule to form an HO3 intermediate which then undergoes fragmentation. No planar transition state for a direct O-atom abstraction could be located. The radical-radical O+HO2 reaction was found to have no energy barrier to formation of HO3 which was determined to subsequently decompose to HO+O2. The H-atom abstraction reaction O+HO2→OH+O2 was found to have a small activation energy. The dynamical implications of these findings are discussed. The results are consistent with the observed vibrational excitation of the OH product in the H+O3 reaction. The key features of the H+O3 potential energy surface are expected to be transferable to the X+O3 systems where X=Cl, OH, NO, and NH2.

Original languageEnglish
Pages (from-to)2691-2697
Number of pages7
JournalJournal of Chemical Physics
Volume84
Issue number5
Publication statusPublished - 1985

Fingerprint

Potential energy surfaces
Wave functions
Atoms
Ozone
potential energy
Energy barriers
wave functions
atoms
Activation energy
ozone
fragmentation
Molecules
activation energy
products
electronics
excitation
molecules
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Dupuis, M., Fitzgerald, G., Hammond, B., Lester, W. A., & Schaefer, H. F. (1985). Theoretical study of the H+O3↔OH+O2↔ O+HO2 system. Journal of Chemical Physics, 84(5), 2691-2697.

Theoretical study of the H+O3↔OH+O2↔ O+HO2 system. / Dupuis, Michel; Fitzgerald, G.; Hammond, B.; Lester, W. A.; Schaefer, H. F.

In: Journal of Chemical Physics, Vol. 84, No. 5, 1985, p. 2691-2697.

Research output: Contribution to journalArticle

Dupuis, M, Fitzgerald, G, Hammond, B, Lester, WA & Schaefer, HF 1985, 'Theoretical study of the H+O3↔OH+O2↔ O+HO2 system', Journal of Chemical Physics, vol. 84, no. 5, pp. 2691-2697.
Dupuis M, Fitzgerald G, Hammond B, Lester WA, Schaefer HF. Theoretical study of the H+O3↔OH+O2↔ O+HO2 system. Journal of Chemical Physics. 1985;84(5):2691-2697.
Dupuis, Michel ; Fitzgerald, G. ; Hammond, B. ; Lester, W. A. ; Schaefer, H. F. / Theoretical study of the H+O3↔OH+O2↔ O+HO2 system. In: Journal of Chemical Physics. 1985 ; Vol. 84, No. 5. pp. 2691-2697.
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