Reconsideration of the anomalous dielectric behavior of dimethyl sulfoxide in the pure liquid state

Abstract

Although many vibrational spectroscopic studies using infrared absorption and Raman scattering techniques reveal that dimethyl sulfoxide (DMSO) forms intermolecular associations, such as dimers, in the pure liquid state, the results of many dielectric relaxation studies deny the presence of such associations and claim very little orientational correlation between the dipoles of DMSO molecules because of a Kirkwood correlation factor close to unity in the pure liquid state and in solution. Recently, we found reasons for the inconsistency and elucidated the presence of dimeric DMSO associations via dielectric relaxation measurements from 50 MHz to 50 GHz. The dissociation of DMSO dimers is the major dielectric relaxation process with a relaxation time of 19 ps, while the relaxation of monomeric DMSO is a minor mode with a relaxation time of 4.5 ps at 25 °C and slightly increasing strength with increasing temperature.