Barrier softening near the onset of nonactivated transport in supercooled liquids: Implications for establishing detailed connection between thermodynamic and kinetic anomalies in supercooled liquids

Abstract

According to the random first-order transition (RFOT) theory of glasses, the barriers for activated dynamics in supercooled liquids vanish as the temperature of a viscous liquid approaches the dynamical transition temperature from below. This occurs due to a decrease of the surface tension between local metastable molecular arrangements much like at a spinodal. The dynamical transition thus represents a crossover from the low T activated behavior to a collisional transport regime at high T. This barrier softening explains the deviation of the relaxation times, as a function of temperature, from the simple log τ ∝1/sc dependence at the high viscosity to a mode–mode coupling dominated result at lower viscosity. By calculating the barrier softening effects, the RFOT theory provides a unified microscopic way to interpret structural relaxation data for many distinct classes of structural glass formers over the measured temperature range. The theory also provides an unambiguous procedure to determine the size of dynamically cooperative regions in the presence of barrier renormalization effects using the experimental temperature dependence of the relaxation times and the configurational entropy data. We use the RFOT theory framework to discuss data for tri-naphthyl benzene, salol, propanol, and silica as representative systems.