Finite size effect on the existence of the liquid–vapour spinodal curve

Abstract

Fluids interacting with Lennard-Jones and Square Well potentials reach thermodynamic equilibrium forming two coexisting phases when simulated within the liquid–vapour spinodal region. If molecular dynamics simulations in the NVT ensemble are performed on a fluid kept in a cubic cell with periodic boundary conditions, liquid and vapour phases at equilibrium are separated by a process of spinodal decomposition. In the vapour side of the spinodal curve, spherical, cylindrical, and slab type liquid structures are formed, depending on the total density. Under the mentioned conditions, in the liquid side of the spinodal, vapour bubbles with the same shapes, surrounded by liquid, are formed. Results from this work suggest that as the simulation system size increases, the spinodal curve approaches the orthobaric, but it converges to a position closer to the coexistence curve but separated from it. The same thing happens for both potential models simulated. This is in sharp contrast with previous findings by Errington, McDowell, Binder and coworkers, where they conclude that ‘Only for infinitely large systems does the effective spinodal density converge to the macroscopic coexistence vapor density.’