Measuring glass entropies with population annealing

TL;DR

This paper introduces a combined computational approach using population annealing Monte Carlo and thermodynamic integration to measure entropies in glass-forming systems, providing evidence for a thermodynamic glass transition.

Contribution

It presents a novel method for accurately measuring vibrational and configurational entropies in glassy systems, revealing the vanishing of configurational entropy before divergence of pressure.

Findings

Configurational entropy vanishes before pressure diverges.

Thermodynamic glass transition likely exists in the studied system.

Method applicable to various glass-forming systems.

Abstract

We combine population annealing Monte Carlo and several thermodynamic integration techniques to measure equilibrium vibrational and configurational entropies in the metastable fluid regime beyond the dynamic glass transition. We obtain results for a three-dimensional binary mixture hard sphere system. Our results suggest that the configurational entropy vanishes before the equilibrium pressure diverges, which implies that an underlying thermodynamic glass transition exists for this system. The computational methods are general and can be applied to a variety of glass forming systems but are restricted to small system sizes.