LAUSR

Abstract Geometrical structure, stability of complexes of acetone/thioacetone with CO2 and/or H2O are thoroughly studied, and the role of intermolecular interactions are determined at the high level of theory. Obtained results propose that the minima of acetone⋯1,2CO2 are mainly stabilized by C⋯O tetrel bond, while in case of thioacetone, the structures are balanced by not only C⋯O tetrel bond, but also C⋯S one and hydrogen bonds. For the rest of investigated systems with the presence of H2O, O H⋯O/S hydrogen bond along with an additional contribution of other weak interactions determine on complex stabilization. The complexes of CO2 and/or H2O with acetone are more stable than those with thioacetone, and the larger positive cooperativity is considerably enhanced with an addition of H2O as compared to CO2 molecule in the acetone/thioacetone⋯CO2/H2O binary complexes. The electrostatic energy is found to be the main term overcoming dispersion and induction components contributing to strength of complexes.