Ultraviolet and laser photolysis of dilute argon matrix samples containing O3and H2S molecules at 8deg;K produced new infrared absorptions at 3425.0, 1177.0, 763.0, and 444.8 cmminus;1which were assigned to the previously unobserved HSOH intermediate species, hydrogen thioperoxide. The HSOH molecule is believed to be formed by the following reaction in the argon matrix cage; lcub;O+H2Srarr;lsqb;H2S=Orsqb;rarr;HSO+Hrarr;HSOHrcub;cage. Extensive18O and deuterium isotopic studies had shown this species to contain one oxygen atom and two nonequivalent hydrogen atoms, while the observation of the Sndash;O stretching vibration at 763.0 cmminus;1had confirmed the presence of a sulfurndash;oxygen single bond. The intense bluehyphen;violet chemiluminescence which appeared when the photolyzed matrix samples were warmed to 20deg;K was subsequently identified as SO2phosphorescence (3B1rarr;1A1). Fluorescence from1B1rarr;1A1was not observed.
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