Probing microhydration-induced effects on carbonyl compounds

Characterizing the microhydration of organic molecules is a crucial step in understanding many phenomena relevant to atmospheric, biological, and industrial applications. However, its precise experimental and theoretical description remains a challenge. For four organic solutes containing a CO bond, and included in the recent HyDRA challenge [T. L. Fischer, M. Bödecker, A. Zehnacker-Rentien, R. A. Mata and M. A. Suhm, Phys. Chem. Chem. Phys., 2022, 24, 11442-11454.], we performed a detailed study of different monohydrate isomers and their properties; these were cyclooctanone (CON), 1,3-dimethyl-2-imidazolidinon (DMI), methyl lactate (MLA), and 2,2,2-trifluoroacetophenone (TPH) molecules. As reported in the literature, the O-H elongation shift of the water molecule appears to be a good candidate for characterizing complexation-induced effects. We also show that CO elongation shift and UV-vis spectroscopy can be successfully used for these purposes. Besides, we present a comparative analysis of the strengths of non-covalent interactions within these monohydrated complexes based on interpretative tools of quantum chemistry, including topological analysis of electron density (ρ), topological analysis of electron pairing function, and analysis of the core-valence bifurcation index (CVBI), which exhibits a close linear dependency on ρ. Accordingly, a classification of intermolecular water-solute interactions is proposed.