Torsional splittings in the diode laser slit-jet spectra of the ν6 fundamental of 1-chloro-1,1-difluoroethane (HCFC-142b)

High resolution infrared spectra (0.001 cm−1 FWHM) have been measured for mixtures of 1-chloro-1,1-difluoroethane in Ne, expanded in a supersonic planar jet. The ν6 fundamental, infrared active with a dominant parallel transition moment, exhibits a remarkable splitting of about 0.035 cm−1 for both 35Cl and 37Cl isotopomers. Several mechanisms of interaction of ν6 with states with high torsional excitation are critically examined to explain the observed effect. It is concluded that the observed torsional splitting patterns can be explained in terms of a torsional Coriolis interaction between ν6 and a highly excited torsional mode, 6ν18. A full numerical analysis, performed including a torsional Coriolis term in the Hamiltonian, shows that the interaction mechanism requires a torsional barrier height of about 1270 cm−1.