Matrix reactions of oxygen atoms with H2S molecules

Abstract

Ultraviolet and laser photolysis of dilute argon matrix samples containing O3 and H2S molecules at 8°K produced new infrared absorptions at 3425.0, 1177.0, 763.0, and 444.8 cm−1 which 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; {O+H2S→[H2S=O]→HSO+H→HSOH}cage. Extensive 18O and deuterium isotopic studies had shown this species to contain one oxygen atom and two nonequivalent hydrogen atoms, while the observation of the S–O stretching vibration at 763.0 cm−1 had confirmed the presence of a sulfur–oxygen single bond. The intense blue-violet chemiluminescence which appeared when the photolyzed matrix samples were warmed to 20°K was subsequently identified as SO2 phosphorescence (3B1→1A1). Fluorescence from 1B1→1A1 was not observed.