Rotational Spectroscopy of the Acetone‐Water Complex: Large Amplitude Motions

Abstract

AbstractAcetone (CH3COCH3), the simplest ketone, has recently attracted considerable attention for its important role in atmospheric chemistry and in the formation of ices in extraterrestrial sources that contain complex organic molecules. In this study, we employed a combination of experimental rotational spectroscopy and quantum chemistry calculations to investigate the structure and dynamics of the acetone‐water complex. Our aim was to understand how non‐covalent interactions with water affect the methyl internal rotation dynamics of acetone, and how water‐centered large amplitude motions alter the observed physical properties compared to those predicted at the equilibrium position. Detailed rotation‐tunneling analyses of acetone‐H2O and ‐D2O reveal that the interactions with water disrupt the equivalence of the two methyl rotors, resulting in a noticeably lower methyl rotor barrier for the top with the close‐by water compared to that of free acetone. The barrier for the methyl group further from water is also lower, although to a lesser degree. To gain further insights, extensive theoretical modelling was conducted, focusing on the associated large amplitude motions. Furthermore, quantum theory of atoms in molecules and non‐covalent interactions analyses were utilized to visualize the underlying causes of the observed trends.