Liquid-vapour asymmetry in pure fluids: A Monte Carlo simulation study

Abstract

Monte Carlo simulations within the grand canonical ensemble are used to obtain the joint distribution of density and energy fluctuations $p_L(\rho,u)$ for two model fluids: a decorated lattice gas and a polymer system. In the near critical region the form of $p_L(\rho,u)$ is analysed using a mixed field finite-size-scaling theory that takes account of liquid-vapour asymmetry. Field mixing transformations are performed that map $p_L(\rho,u)$ onto the joint distribution of critical scaling operators \ptMEstar\ appropriate to the Ising fixed point. Carrying out this procedure permits a very accurate determination of the critical point parameters. By forming various projections of \ptMEstar , the full universal finite-size spectrum of the critical density and energy distributions of fluids is also obtained. In the sub-critical coexistence region, an examination is made of the influence of field mixing on the asymmetry of the density distribution.