ChemInform Abstract: Chemiluminescence Spectra of Thioformaldehyde and Selenoformaldehyde.

Abstract

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