Journal of Chemical Physics, Vol.101, No.1, 31-38, 1994
Determination of the Spectroscopic Constants of a Dark Vibrational-State - Fermi and Coriolis Perturbations in the Nu-2 Band of Formyl Chloride
The nu(2) infrared fundamental of the transient molecule formyl chloride, HCOCl, has been recorded at high resolution. Detailed assignments of the rotational structure have been made for both HCO Cl-35 and (HCOCl)-Cl-37. The nu(2) band, whose origin is at 1784.1377 cm(-1) in (HCOCl)-Cl-35, is predominantly A type with a very weak B-type component. Numerous excited state perturbations occur throughout the band, caused mainly by Delta K-a=2 Fermi resonance and Delta K-a=1 Coriolis interactions with the 3(1)5(1) vibrational state. Even though no "extra" lines resulting from the perturbations could be assigned, a complete analysis of the perturbed rotational structure has been possible. Accurate molecular constants for both the "bright" perturbed 2(1) state and the "dark" 3(1)5(1) perturbing state have been obtained, using a Hamiltonian which includes both the Fermi and Coriolis interactions; only two interaction parameters are needed, one for each mechanism. Further perturbations at high K-a are assigned to Coriolis interactions with the 5(2)6(1) level.