A method to compute absolute free energies or enthalpies of fluids

TL;DR

This paper introduces a novel simulation-based method for calculating the free energy and enthalpy of fluids and disordered solids by constructing a reference system and performing thermodynamic integration, even in the presence of particle diffusion.

Contribution

It presents a new algorithm for sampling thermodynamic paths in liquids, enabling accurate free energy calculations for fluids and solids with mobile defects.

Findings

Successfully applied to hard sphere fluids

Effective in systems with mobile defects

Provides a detailed strategy for thermodynamic integration

Abstract

We propose a new method to compute the free energy or enthalpy of fluids or disordered solids by computer simulation . The main idea is to construct a reference system by freezing one representative configuration, and then carry out a thermodynamic integration. We present a strategy and an algorithm which allows to sample the thermodynamic integration path even in the case of liquids, despite the fact that the particles can diffuse freely through the system. The method is described in detail and illustrated with applications to hard sphere fluids and solids with mobile defects.