INFRARED SPECTRUM OF THE $FO_{2}$ RADICAL

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1987

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Ohio State University

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$FO_{2}$ has previously been observed by infrared and ESR techniques in low temperature matrices, but the first gas-phase spectroscopy was reported only recently by Yamada and $Hirota^{1}$ who studied the $\nu_{3}$ band at $579 cm^{-1}$ using a tunable diode laser spectrometer. We have now recorded and analyzed the $\nu_{1}, 2\nu_{1}, 2\nu_{3}, \nu_{2}+\nu_{3}$, and $\nu_{2}+2\nu_{3}$ bands as well as the previously studied $\nu_{3}$ fundamental. The experiments were performed in Boulder using a high-resolution $(0.0026 cm^{-1})$ Bomem FTS and a fast-flow long-path absorption cell: $FO_{2}$ was produced using the reaction $F + O_{2} + M FO_{2} + M$. The most interesting aspect of the analysis is the region of the $\nu_{1}$ fundamental: it turns out that $\nu_{1} (1487 cm^{-1})$ is very strongly perturbed by $\nu_{2}+2\nu_{3} (1496 cm^{-1})$ through both Coriolis and homogeneous (Fermi-type) interactions. In contrast, the other bands $\nu_{3}, \nu_{2}+\nu_{3} (940 cm^{-1}), 2\nu_{3} (1142 cm^{-1})$ were found to be unperturbed. $2\nu_{1} (2948 cm^{-1})$ is apparently subject to a number of smaller perturbations, but it could be approximately analyzed without including them. Our work yields an extensive set of molecular parameters for $FO_{2}$, including approximate spin-rotation constants for the states involved. Now only the $\nu_{2}$ fundamental $(=370 cm^{-1}7)$ remains unobserved at high resolution.

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$^{1}$ C. Yamada and E. Hirota, J. Chem. Phys. 80, 4694 (1984).
Author Institution: Herzberg Institute of Astrophysics, National Research Council of Canada; NOAA Aeronomy Laboratory, University of Colorado

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