Barrier Softening near the onset of Non-Activated Transport in Supercooled Liquids: Implications for Establishing Detailed Connection between Thermodynamic and Kinetic Anomalies in Supercooled Liquids

TL;DR

This paper explores how barrier softening near the dynamical transition in supercooled liquids explains deviations in relaxation times from simple models, providing a unified microscopic interpretation across various glass formers.

Contribution

It introduces a detailed RFOT-based framework for understanding barrier softening and its impact on relaxation dynamics in supercooled liquids, linking thermodynamic and kinetic anomalies.

Findings

Barrier softening occurs near the dynamical transition temperature.

The theory unifies interpretation of relaxation data across different glass formers.

Provides a method to estimate cooperative region sizes from experimental data.

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 meta-stable molecular arrangements much like at a spinodal. The dynamical transition thus represents a crossover from the low $T$ activated bevavior 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 $\log \tau \propto 1/s_c$ 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 {\em 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.