Molecular dynamics (MD) simulations of pure dimethyl sulphoxide (DMSO) and solutions of Na+, Ca2+, Cl−, NaCl and CaCl2 in DMSO have been performed at 298.15 K and 398.15 K in NVT ensembles by using a four-interaction-site model of DMSO and reaction field method for Coulombic interactions. The structure of solvent, ion-solvation shells and ion-pairs have been analysed by employing a concept of coordination centres and characteristic vectors of the solvent molecule. Results are given for atom-atom (corresponding to DMSO), ion-atom and ion-ion radial distribution functions (RDFs), orientation of the DMSO molecules and their geometrical arrangements in the first solvation shells of the ions (Na+, Ca2+, Cl−). A preferential formation of cyclic dimers with antiparallel alignment between dipole moments of nearest-neighbour molecules in the pure solvent is found. Geometrical models of the first coordination shells of the ions in ‘infinitely dilute solutions’ are proposed. Ion-ion RDFs in NaCl-DMSO and CaCl2-DMSO solutions reveal the presence of both solvent separated (SSIP) and contact (CIP) ion pairs. The structures of the solvation shells of such ion pairs are also discussed.
Adya, A. K., Kalugin, O. N., Volobuev, M. N., & Kolesnik, Y. V. (2001). Microscopic structure of liquid dimethyl sulphoxide and its electrolyte solutions: molecular dynamics simulations. Molecular Physics, 99(10), 835-854. https://doi.org/10.1080/00268970010024867