Secondary Water Relaxation in a Water/Dimethyl Sulfoxide Mixture Revealed by Deuteron Nuclear Magnetic Resonance and Dielectric Spectroscopy

Abstract

We exploit the potential of a combined dielectric spectroscopy (DS) and deuteron nuclear magnetic resonance ((2)H NMR) approach to investigate the molecular dynamics in a supercooled 2:1 molar mixture of deuterated water (D(2)O) and dimethyl sulfoxide (DMSO). While DS probes the rotational motion of both components, application of (2)H NMR allows us to single out the dynamical behavior of the water molecules. Combining the results of both methods, we can follow the slowdown of the α-process of the mixture over more than 10 orders of magnitude in time, revealing that the Vogel-Fulcher-Tammann (VFT) equation describes well its temperature dependence down to the glass transition temperature, T(g) = 146 K. While the (2)H NMR data do not provide evidence for a secondary relaxation process in the weakly supercooled regime, they indicate that, in the deeply supercooled regime, T(g) ≤ T ≤ 160 K, the water molecules do show a secondary dynamical process, which is faster and exhibits a weaker temperature dependence than the α-process of the mixture. Consistently, the shape of the dielectric spectra changes in this temperature range. (2)H NMR rotational correlation functions reveal that this faster secondary water process destroys essentially all orientational correlation. In addition, these data show that the water reorientation process is characterized by a mean elementary jump angle smaller than 13°. Possible origins of the faster secondary water process in the deeply supercooled mixture are discussed.