Phase behavior of a confined nano-droplet in the grand-canonical ensemble: the reverse liquid-vapor transition

Abstract

The equilibrium density distribution and thermodynamic properties of a Lennard-Jones fluid confined to nano-sized spherical cavities at constant chemical potential was determined using Monte Carlo simulations. The results describe both a single cavity with semipermeable walls as well as a collection of closed cavities formed at constant chemical potential. The results are compared to calculations using classical Density Functional Theory (DFT). It is found that the DFT calculations give a quantitatively accurate description of the pressure and structure of the fluid. Both theory and simulation show the presence of a ``reverse'' liquid-vapor transition whereby the equilibrium state is a liquid at large volumes but becomes a vapor at small volumes.

13 pages, 8 figures, to appear in J. Phys. : Cond. Matt

References in corpus (4)

• Dependence of the liquid-vapor surface tension on the range of interaction: a test of the law of corresponding states
• Density Functional Theory of Inhomogeneous Liquids: III. Liquid-Vapor Nucleation
• Density Functional Theory of Inhomogeneous Liquids: II. A Fundamental Measure Approach
• Calculations of canonical averages from the grand canonical ensemble

Cited by in corpus (2)

• Density Functional Theory of Inhomogeneous Liquids IV. Squared-gradient approximation and Classical Nucleation Theory
• Generalization of the Wall Theorem to Out-of-equilibrium Conditions