Molecular emission spectra in the visible and near IR produced in the chemiluminescent reactions of molecular fluorine with organosulfur compounds

Rich chemiluminescence is observed in the gas phase reactions of F2 with a variety of organosulfur compounds at room temperature and from 0.2 to 2.0 Torr. HCF(A1A″) and vibrationally excited HF are observed in the reaction of F2 with all the hydrogen-bearing compounds under varying conditions of reactant pressure. For the organosulfur reactants used in this study, CH2S(a 3A2) is observed only with CH3SH, CH3SCH3 and CH3SSCH3. The character of the emission spectra changes dramatically with changing reactant pressures or when CH3OH or CH3CH are present. CH2S* is observed with CH3CH2SH and higher thiols when CH3OH is present. A new vibrationally structured spectral feature appears ubiquitously in all of the reaction systems studied, and distinctly in the reaction of F2 with CS2. It is ascribed to an electronic transition of the transient species, FCS. The initiation of the reactions of F2 with the stable organosulfur species and the implications of this work for IR multiphoton dissociation are discussed.