Excess free energy of supercooled liquids at disordered walls

TL;DR

This paper introduces a new thermodynamic integration method to calculate the excess free energy of a supercooled liquid near an amorphous wall, revealing negative values at low temperatures, which indicates a significant thermodynamic perturbation.

Contribution

The study presents a novel thermodynamic integration scheme for computing excess free energy in supercooled liquids at disordered walls, highlighting the impact of amorphous boundaries.

Findings

Excess free energy becomes negative at low temperatures.

The amorphous wall perturbs the thermodynamics of the supercooled liquid.

The method provides new insights into glass-forming liquids near disordered interfaces.

Abstract

Using a novel thermodynamic integration scheme, we compute the excess free energy, $\gamma$, of a glass-forming, binary Lennard-Jones liquid in contact with a frozen amorphous wall, formed by particles frozen into a similar structure as the liquid. We find that $\gamma$ is non-zero, becoming negative at low temperature. This indicates that the thermodynamics of the system is perturbed by the effect of the amorphous wall.