Ozone and oxygen atom reactions with dimethylsulfide and methanethiol in argon matrices

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Abstract
Ground state oxygen atoms, generated by visible photolysis of ozone, have been reacted with CH3SCH3 and CH3SH in argon matrices. For CH3SCH3, a stepwise addition to form DMSO and dimethylsulfone was observed. Methanethiol reactions with O atoms were more complex, leading to production of CH3SOH, CH3OSH, CH3S(O)H, and possibly CH3–SO2–H. These results are compared to the O+H2S reaction. The matrix results are also compared to gas phase studies where more extensive fragmentation has been observed, and inferences are drawn concerning the relative matrix deactivation rates of the highly energetic sulfide–oxygen-atom precursor complex.