THEORETICAL AND EXPERIMENTAL EVIDENCE FOR THE METASTABLE BOUND CYCLIC CONFORMER OF OZONE AND ITS ROLE IN OZONE CHEMISTRY
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Date
1977
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Ohio State University
Abstract
We have recently surveyed the potential surface of the ground state of ozone, and applied new techniques for generating very highly correlated wave-functions to a study of the electronic structure, geometry and properties of species corresponding to the local minima on this surface, bent and cyclic ozone. Despite recent statements to the $contrary,^{1}$ we find the cyclic species to be significantly bound with respect to dissociation to $O_{2} + O$ in their ground states. This species is consistent with the properties of the $O_{3}^{\alpha}$ intermediate observed in $O_{2} + O$ (ground states) recombination $experiments.^{2}$ Our predictions are based on large basis Coupled Electron Pair Approximation-Pair Natural Orbital (CEPA-PNO) computations which go systematically beyond double excitation configuration interaction. Our wave-functions for each species have significantly lower ($\stackrel{>}{\sim}$ 4.5 eV) total energies than previous models and the credibility of our prediction is enhanced by the accuracy of the structural computation of the bent ozone ground state (within 0.8 pm and $0.5^\circ$ for r(0--0) and angle).
Description
$^{1}$P. J. Hay, T. H. Dunning, and W. A. Goddard, J. Chem. Phys. 62, 3912 (1975). $^{2}$P.L.T. Bevan and G.R.A, Johnson, Farad. Trans. I. 69, 216 (1973).
Author Institution: Department of Chemistry, University of Wollongong; Laboratory of Chemical Physics, California Institute of Technology
Author Institution: Department of Chemistry, University of Wollongong; Laboratory of Chemical Physics, California Institute of Technology