Analysis of the Coriolis perturbed rovibrational spectrum of the CO asymmetric stretch and CC symmetric stretch of trimethylene oxide

Thumbnail Image
Date
2020-06-12
Authors
Mahassneh, Omar
van Wijngaarden, Jennifer
Journal Title
Journal ISSN
Volume Title
Publisher
Journal of Molecular Spectroscopy
Abstract
Rotationally-resolved vibrational spectra of trimethylene oxide (c-C3H6O) were recorded using synchrotron radiation from the Canadian Light Source between 400 and 1200 cm−1 with a resolution of 0.000959 cm−1. The dense spectra are composed of transitions arising from excitation of several fundamental vibrations as well as hotbands and combination bands involving the very low frequency ring puckering (ν18) vibration at ~53 cm−1. To date, 3452 transitions have been assigned corresponding to the CO asymmetric stretch (ν23) at ~1008 cm−1 and the CC symmetric stretch (ν6) at ~1033 cm−1 which are coupled via second order c-type Coriolis interaction. An additional perturbation from a lower energy state was observed and attributed to a first order b-type interaction with a state that is likely the combination of the CC asymmetric stretching (ν24) at ~937 cm−1 and ring puckering motions. An additional 916 transitions involving the CO stretching mode were assigned to two hotbands that originate in the first and second excited ring puckering states of trimethylene oxide. Accurate band centers for the ν6, ν23, ν23 + ν18, ν23 + 2ν18 and ν24 + ν18 vibrational states were determined and are compared with harmonic and anharmonic frequency estimates at the MP2 and DFT B3LYP levels using the 6-311++G(d,p) basis set. The analysis of additional features at lower frequency is in progress and will be reported in a subsequent article.
Description
Keywords
oxetane, rovibrational spectroscopy, Synchrotron, Infrared, Coriolis interaction, ring puckering, frequency calculations
Citation
Mahassneh, O.; van Wijngaarden, J. Analysis of the Coriolis perturbed rovibrational spectrum of the CO asymmetric stretch and CC symmetric stretch of trimethylene oxide. J. Mol. Spectrosc. 2020, 371, 111322.