The 290-nm absorption system of propiolyl fluoride

The vapor-phase absorption spectrum of propiolyl fluoride HCCCOF and deuterio-propiolyl fluoride has been examined under medium resolution in the region from 303 to 260 nm. While considerable vibrational structure is evident, all bands are found to be rotationally diffuse. The electronic transition is identified as the singlet-singlet $\text{π}{}^1\text{← n}$ transition analogous to the 382-nm system of propynal. The evidence for a nonplanar excited-state geometry is discussed. The principal excited-state vibrational frequencies identified are 158 (ν′₉), 396 (ν′₈), and 1222 cm^?1 (ν′₃) for HCCCOF. The corresponding values for DCCCOF are 150, 390, and 1217 cm^?1, respectively. The triplet ← singlet system involving the same electron promotion has not been found.