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

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 (Robles M. and LOPEZ DE HARO M., Phys. Chem. Chem. Phys., 3 (2001) 5528) 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 R. et al., Phys. Rev. Lett., 84 (2000) 6054) is obtained.