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

Journal Article · Sat Mar 01 04:00:00 EST 1986 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.450342· OSTI ID:6240937

Dupuis, M; Fitzgerald, G; Hammond, B; Lester, Jr, W A; Schaefer, III, H F

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.

• Research Organization: Materials and Molecular Research Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6240937
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 84:5; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ATMOSPHERIC CHEMISTRY
CHEMICAL REACTIONS
CHEMISTRY
COMBUSTION
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY
HYDROGEN
MECHANICS
NONMETALS
OXIDATION
OZONE
POTENTIAL ENERGY
QUANTUM MECHANICS
REACTION INTERMEDIATES
THERMOCHEMICAL PROCESSES