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Moderate-resolution chemiluminescence spectra of CD{sub 2}S, CH{sub 2}S, and CH{sub 2}Se were obtained during the reaction of F{sub 2} with methylated sulfur and selenium compounds at about 0.5 Torr of total pressure. Phosphorescence corresponding to the {tilde a}{sup 3}A{sub 2} {yields} {tilde X}{sup 1}A{sub 1} transition dominated all the spectra, and a trace of fluorescence, {tilde A}{sup 1}A{sub 2} {yields} {tilde X}{sup 1}A{sub 1}, appeared only in the spectrum of CH{sub 2}Se. The v{sub 4} and v{sub 6} frequencies of the {tilde a} state of CD{sub 2}S are reported for the first time as 219.4 {plus minus} 5.0 and 572.6 {plus minus} 5.0 cm{sup {minus}1}, respectively. From the unusually shaped 4{sub 1}{sup 1} band of CH{sub 2}S ({tilde a} {yields} {tilde X}) an improved value of the v{prime}{sub 4} frequency was found to be 308 {plus minus} 30 cm{sup {minus}1}. The CH{sub 2}Se yielded an improved measurement of the v{double prime}{sub 3} frequency, 860 {plus minus} 10 cm{sup {minus}1}, and new estimates of three other ground-state frequencies: v{double prime} = 1,460 {plus minus} 30, v{double prime}{sub 4} = 906 {plus minus} 10, and v{double prime} = 914 {plus minus} 10, and v{double prime}{sub 6} = 914 {plus minus} 20 cm{supmore » {minus}1}. A spectrum of CH{sub 2}Te was sought in the reactions of CH{sub 3}TeCH{sub 3} and CH{sub 3}Te{sub 2}CH{sub 3} with F{sub 2} but was not found; instead emission from TeF (A{sup 2}{pi}{sub i} {yields} X{sup 2}{pi}{sub 1}) was observed.« less

The spectra from the chemiluminescent reactions of ozone with dimethyl sulfoxide and dimethyl disulfide ((CH/sub 3/S)/sub 2/) have been studied at low pressure in a beam-gas apparatus. The chemiluminescence emission for each reaction was monitored as a function of the ozone and fuel pressures over a total pressure range from 0.05 to 50 mtorr. In the reaction of ozone with dimethyl sulfoxide weak, unstructured emission was observed in the region from 280 to 500 nm. This emission was found to be congruent to that observed in the reactions of ozone with H/sub 2/S, CH/sub 3/SH, and CH/sub 3/SCH/sub 3/ under similar conditions and was attributed to fluorescence from electronically excited SO/sub 2/. The reaction of ozone with (CH/sub 3/S)/sub 2/ also yielded broad-band fluorescence from SO/sub 2/ as well as a vibrationally resolved SO/sub 2/ phosphorescence feature. Chemiluminescence from the HSO radical was observed to the red of 530 nm in the reaction of ozone with (CH/sub 3/S)/sub 2/. Mechanisms have been proposed for each reaction based on the character of the luminescence and the dependence of the emission on reactant pressure. Results are contrasted with previous work on other simple sulfides. 25 references, 8 figures.