Assignment of the Fundamental Modes of Hydroxyacetone Using Gas-Phase Infrared, Far-Infrared, Raman, and <i>ab Initio</i> Methods: Band Strengths for Atmospheric Measurements

Hydroxyacetone (acetol) is a simple organic molecule of interest in both the astrophysical and atmospheric communities. It has recently been observed in biomass burning events and is a known degradation product of isoprene oxidation. However, its vibrational assignment has never been fully completed, and few quantitative data are available for its detection via infrared spectroscopy. Our recent acquisition of both the pressure-broadened gas-phase data and the far-IR spectra now allow for unambiguous assignment of several (new) bands. In particular, the observed C-type bands of several fundamentals (particularly in the far-infrared) and a few combination bands demonstrate that the monomer is in a planar (<i>C</i>_<i>s</i>) conformation, at least a majority of the time. As suggested by other researchers, the monomer is a <i>cis–cis</i> conformer stabilized by an intramolecular OH···OC hydrogen bond forming a five-membered planar ring structure. Band assignments in the <i>C</i>_<i>s</i> point group are justified (at least for a good fraction of the molecules in the ensemble) by the presence of the C-type bands. The results and band assignments are well confirmed by both <i>ab initio</i> MP2-ccpvtz calculations and GAMESS (B3LYP) theoretical calculations. In addition, using vetted methods for quantitative measurements, we report the first IR absorption band strengths of acetol (also in electronic format) that can be used for atmospheric monitoring and other applications