Terahertz dynamics in the glycerol-water system

Abstract

The model glass former glycerol and its aqueous mixtures were investigated with terahertz-time-domain spectroscopy (THz-TDS) in the frequency range 0.3--3.0 THz at temperatures from 80 to 305 K. It was shown that the infrared absorption coefficient measured with THz-TDS can be theoretically related to the reduced Raman intensity ($\ensuremath{\propto}\ensuremath{\alpha}/{\ensuremath{\omega}}^{2}$) and the reduced density of states ($\ensuremath{\propto}\ensuremath{\alpha}/{\ensuremath{\omega}}^{3}$) and the agreement with experimental results confirms this. The data were further used to investigate the behavior of model glasses in the harmonic (below the glass transition temperature ${T}_{\text{g}}$), anharmonic (above ${T}_{\text{g}}$), and liquid regimes. The onset temperature of molecular relaxation as measured by the infrared active dipoles, ${T}_{\text{g}}$, was found to correlate with the onset of anharmonic effects, leading to an apparent shift of the boson peak and obscuring it at elevated temperatures. The influence of clustered and unclustered water on the dynamics, the boson peak, and the vibrational dynamics was also investigated. A change in structural dynamics was observed at a water concentration of approximately 5 wt %, corresponding to a transition from isolated water molecules distributed homogeneously throughout the sample to the presence of small water clusters and an increased number of water-water hydrogen bonds which lower the barriers on the potential energy surface.