Synchrotron-based far-infrared spectroscopic investigation and ab initio calculations of 3-oxetanone: observation and analysis of the ν7 band and the Coriolis coupled ν16 and ν20 bands.

ABSTRACT

Rotationally resolved vibrational spectra of the four-membered heterocycle 3-oxetanone (c-C(3)H(4)O(2)) have been investigated in the 360-720 cm(-1) region with a resolution of 0.000 959 cm(-1) using synchrotron radiation from the Canadian Light Source. The observed bands correspond to motions best described as C═O deformation out-of-plane (ν(20)) at 399.6 cm(-1), C═O deformation in-plane (ν(16)) at 448.2 cm(-1), and the ring deformation (ν(7)) at 685.0 cm(-1). Infrared ground state combination differences along with previously reported pure rotational transitions were used to obtain the ground state spectroscopic parameters. Band centers, rotational and centrifugal distortion constants for the ν(7), ν(16), and ν(20) vibrational excited states were accurately determined by fitting a total of 10,319 assigned rovibrational transitions in a global analysis. The two adjacent carbonyl deformation bands, ν(16) and ν(20), were found to be mutually perturbed through a first-order a-type Coriolis interaction which was accounted for in the multiband analysis. The band centers agree within 3% of the ab initio estimates using DFT theory.