Intermolecular Forces and the Glass Transition

TL;DR

This paper uses a theoretical framework combining random first order transition theory and self-consistent phonon theory to analyze the roles of attractive and repulsive forces in the glass transition, providing predictions for transition temperatures and relaxation behaviors.

Contribution

It introduces a comprehensive microscopic model that predicts various glass transition temperatures and explains empirical density-temperature scaling in supercooled liquids.

Findings

Predicted transition temperatures including $T^{*}_{A}$, $T_{c}^{*}$, $T^{*}_{K}$, and $T^{*}_{g}$.

Reproduced empirical density-temperature scaling relations for relaxation times.

Supported the hypothesis of an intersection between spinodal and Kauzmann temperatures at low temperatures.

Abstract

Random first order transition theory is used to determine the role of attractive and repulsive interactions in the dynamics of supercooled liquids. Self-consistent phonon theory, an approximate mean field treatment consistent with random first order transition theory, is used to treat individual glassy configurations, while the liquid phase is treated using common liquid state approximations. The transition temperature $T^{*}_{A} $, the temperature where the onset of activated behavior is predicted by mean field theory, the lower crossover temperature $T_{c}^{*}$ where barrierless motions actually occur through fractal or stringy motions, and $T^{*}_{K} $, the Kauzmann temperature, are calculated in addition to $T^{*}_{g} $, the glass transition temperature that corresponds to laboratory cooling rates. Both the isobaric and isochoric behavior in the supercooled regime are studied, providing results for $\Delta C_{V} $ and $\Delta C_{p} $ that can be used to calculate the fragility as a function of density and pressure, respectively. The predicted variations in the $\alpha$-relaxation time with temperature and density conform to the empirical density-temperature scaling relations found by Casalini and Roland. We thereby demonstrate the microscopic origin of their observations. Finally, the relationship first suggested by Sastry between the spinodal temperature and the Kauzmann temperatures, as a function of density, is examined. The present microscopic calculations support the existence of an intersection of these two temperatures at sufficiently low temperatures.