Matrix-Isolation Study of the Vacuum-Ultraviolet Photolysis of Chlorofluoromethane. The Infrared and Ultraviolet Spectra of the Free Radical ClCF

Abstract

The vacuum-ultraviolet photolysis of CH2ClF and of CD2ClF isolated in an argon matrix at 14°K leads to the appearance of prominent absorptions at 742 and at 1146 cm−1 which have been assigned to the two stretching fundamentals of ClCF. A weak absorption band system between 3900 and 3400 Å, with a 376 ± 10 cm−1 average band spacing, may be tentatively attributed to ClCF, as may be an emission band system which appears between 4000 and 4900 Å when the sample is excited by 3650-Å radiation. The 379 ± 10 cm−1 average band spacing associated with this emission band system has been tentatively attributed to the bending mode of ground-state ClCF, permitting a normal coordinate analysis for this molecule. The bending and the C–Cl stretching modes are appreciably mixed. Several other groups of absorptions also have been observed in these experiments, but the species responsible for them have not been definitively identified.