The influence of intermolecular correlations on the infrared spectrum of liquid dimethyl sulfoxide

Dimethyl sulfoxide (DMSO) is routinely applied as an excellent, water-miscible solvent and chemical reagent. Some of the most important data concerning its liquid structure were obtained using infrared (IR) spectroscopy. However, the actual extent of intermolecular correlations that connect the isolated monomer spectrum to the IR response of the bulk liquid is poorly studied thus far. Using ab initio molecular dynamics (AIMD) simulations, IR spectra of liquid DMSO are obtained here from first principles and further analyzed using an array of sophisticated spectral decomposition techniques. The calculated spectra when unfolded in space reveal non-trivial spatial correlations underlying the IR response of liquid DMSO. It is unequivocally demonstrated that some of the fundamental vibrations visible in the intramolecular limit are effectively suppressed by the solvation environment due to symmetry reasons and thus disappear in the bulk limit, escaping experimental detection. Overall, DMSO as an aprotic solvent with dominant dipole–dipole interactions displays strong intermolecular correlations that contribute significantly to the IR spectra, on par with the situation observed in strongly associated liquids, such as water.