On the liquid-glass transition line in monatomic Lennard-Jones fluids

TL;DR

This paper presents a thermodynamic method to predict the liquid-glass transition line in monatomic Lennard-Jones fluids, showing good agreement with recent molecular dynamics simulations.

Contribution

It introduces a new thermodynamic approach based on a reformulation of perturbation theory and a rational function approximation for the radial distribution function.

Findings

Accurate prediction of the liquid-glass transition line.

Good agreement with molecular dynamics simulation data.

Uses only an equation of state for the hard-sphere system.

Abstract

A thermodynamic approach to derive the liquid-glass transition line in the reduced temperature vs reduced density plane for a monatomic Lennard-Jones fluid is presented. The approach makes use of a recent reformulation of the classical perturbation theory of liquids [M. Robles and M. L\'opez de Haro, Phys. Chem. Chem. Phys. {\bf 3}, 5528 (2001)] which is at grips with a rational function approximation for the Laplace transform of the radial distribution function of the hard-sphere fluid. The only input required is an equation of state for the hard-sphere system. Within the Mansoori-Canfield/Rasaiah-Stell variational perturbation theory, two choices for such an equation of state, leading to a glass transition for the hard-sphere fluid, are considered. Good agreement with the liquid-glass transition line derived from recent molecular dynamic simulations [Di Leonardo et al., Phys. Rev. Lett. {\bf 84}, 6054(2000)] is obtained.