Computation of the chemical potential and solubility of amorphous solids

TL;DR

This paper investigates methods to accurately compute the chemical potential and solubility of amorphous solids using equilibrium and non-equilibrium simulation techniques, highlighting the effectiveness of Jarzynski's method over traditional thermodynamic integration.

Contribution

It introduces a novel application of Jarzynski's non-equilibrium free energy method to estimate chemical potentials in glasses, improving accuracy over standard approaches.

Findings

Jarzynski's method yields chemical potential estimates consistent with supercooled liquid extrapolations.

Thermodynamic integration shows high scatter and overestimates chemical potentials.

Amorphous solubility decreases over time, aligning qualitatively with experimental observations.

Abstract

Using a recently developed technique to estimate the equilibrium free energy of glassy materials, we explore if equilibrium simulation methods can be used to estimate the solubility of amorphous solids. As an illustration, we compute the chemical potentials of the constituent particles of a two-component Kob-Andersen model glass former. To compute the chemical potential for different components, we combine the calculation of the overall free energy of the glass with a calculation of the chemical potential difference of the two components. We find that the standard method to compute chemical potential differences by thermodynamic integration yields not only a wide scatter in the chemical potential values but, more seriously, the average of the thermodynamic integration results is well above the extrapolated value for the supercooled liquid. However, we find that if we compute the difference of the chemical potential of the components with the the non-equilibrium free energy expression proposed by Jarzynski, we obtain a good match with the extrapolated value of the supercooled liquid. The extension of the Jarzynski method that we propose opens a potentially powerful route to compute free-energy related equilibrium properties of glasses. We find that the solubility estimate of amorphous materials obtained from direct coexistence simulations is only in fair agreement with the solubility prediction based on the chemical potential calculations of a hypothetical "well-equilibrated glass". In direct coexistence simulations, we find that, in qualitative agreement with experiments, the amorphous solubility decreases with time and attains a low solubility value.