THE LOW-LYING STATFS OF THE POSITIVE AND NEGATIVE IONS OF OZONE

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1976

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Ohio State University

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Ab initio configuration interaction calculations will be reported on the low-lying states of the positive and negative ions at ozone. In agreement with the experimental $studies,^{1}$ we find the lowest state of $O^{+}_{3}$ to be $^{2}A_{1}$; the $^{2}B_{1}$ state is found to lie nearby with the $^{2}A_{2}$ state, which the Hartree-Fock method predicts to be the lowest ion state, $1/2-1$ eV higher. Besides these three ion states so prominent in the photoelectron spectra of ozone, the calculations predict several ""shake-up"" states, involving ionization and excitation, within 5 eV of the lowest ionic state. The $^{2}B_{1}$ state is found to be the ground state of $O^{-}_{3}$, with a $(^{2}A_{1}, ^{2}B_{2})$ nearly degenerate pair next and a $^{2}A_{2}$ state highest. The calculations suggest that the electronic transition of $O^{-}_{3}$ observed in matrix isolation is a $^{2}A_{1} - X^{2}B_{1}$ transition.

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$^{1}$ L.E. Brus, Chem. Phys. Lett. 12, 116 (1971). $^{2}$ Ch. Jungen, D.N. Malm, and A.J. Merer, Chem. Phys, Lett. 16, 302 (1972).
Author Institution: Los Alamos Scientific Laboratory, University of California

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