Hydrogen Bonding in Glycerol and Dimethyl Sulfoxide Complexes

Quantum chemical calculations of glycerol and dimethylsulfoxide dimers, as well as glycerol–dimethylsulfoxide complexes of 1:1, 2:1, 1:2, 3:1, 1:3 compositions, with and without solvation were carried out using the integral equation formalism model IEFPCM by means of the density functional theory DFT method with the hybrid three-parameter Becke, Lee–Yang–Parr functional B3LYP taking into account the Grimme dispersion correction D3 and the Pople basis set 6-311++G(d,p), which includes both polarization and diffusion functions, using the Gaussian 16 software package. The interaction energies were calculated taking into account the basis sets superposition correction. The contributions of dispersion interactions to the interaction energy were calculate as the difference between the interaction energies with and without the dispersion correction. Geometrical and topological parameters of H-bonds were calculated using the methods of natural bond orbital analysis – Weinhold’s NBO and Bader’s quantum theory of atoms in a molecule QTAIM. It was shown that in the studied system various bonds can be formed, both classical hydrogen О–H···O bonds and C–H···O, O···O, O···S and C–H···S interactions. Intermolecular hydrogen bonds O–H···O between glycerol molecules are stronger than intramolecular H-bonds O–H···O. Contributions of dispersion interactions in glycerol–dimethyl sulfoxide complexes are 30–40%, in the case of glycerol dimers – 30%. In dimethyl sulfoxide dimers, this contribution is maximum: from 40% to 60%. Dimethyl sulfoxide molecules are embedded in the network of hydrogen bonds of glycerol. Taking solvation into account leads to strengthening of intermolecular bonds O–H···O and weakening of other intermolecular interactions. In some cases, a rupture of weak intermolecular bonds C–H···O and intramolecular bonds O–H···O is observed. For citation: Kruglyakova A.A., Krestyaninov M.A., Nikitin M.E., Egorov G.I. Hydrogen bonding in glycerol and dimethyl sulfoxide complexes. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2025. V. 68. N 10. P. 46-57. DOI: 10.6060/ivkkt.20256810.7180.