INFRARED SPECTRUM OF $O_{3}^{-}$ ISOLATED IN SOLID NEON AND EVIDENCE FOR THE STABILIZATION OF $O_{2}\cdots{O}_{4}^{+}$

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1996

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Ohio State University

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When a $Ne:O_{3}$ sample is codeposited at approximately 5 K with neon atoms that have been excited in a microwave discharge, the most prominent infrared absorptions of the resulting solid are contributed by trans- and cyc-$O_{4}^{+}$ and by $O_{3}^{-}$. The failure to detect infrared absorptions of $O_{3}^{+}$ is consistent with the initial formation of that species in one or more dissociative excited states. The $\nu_{3}$ absorption of $O_{3}^{-}$ appears at $796.3 cm^{-1}$, close to its position in earlier argon-matrix experiments in which photoionization of an alkali metal atom provided the electron source and in which diffusion of the atomic cation would result in the stabilization of appreciable $M^{+}O_{3}$. The identification of $O_{3}^{-}$ isolated in solid neon is supported by observations of $O_{3}^{-}$ generated from isotopically substituted Ne:$O_{2}:N_{2}O$ samples, also codeposited with excited neon atoms. An upper bound of $810 cm^{-1}$ is estimated for the gas-phase band center of $\nu_{3}$ of $O_{3}^{-}$. Infrared absorptions which grow on mild warmup of the sample are tentatively assigned to an $O_{2}\cdots{O}_{4}^{+}$ complex.

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Author Institution: Molecular Physics Division, National Institute of Standards and Technology

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