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

2009/11/17 by James F. Lutsko, Julien Laidet, Patrick Grosfils · 1 citation
Chemistry · Engineering · Materials Science · Physics and Astronomy · #Advanced Thermodynamics and Statistical Mechanics #Canonical ensemble #Chemical physics #Chemistry #Classical mechanics #Computational chemistry #Constant (computer programming) #Density functional theory #Grand canonical ensemble #Lennard-Jones potential #Material Dynamics and Properties #Molecular dynamics #Monte Carlo method #Phase Equilibria and Thermodynamics #Phase transition #Physics #Reaction rate constant #Statistical physics #Thermodynamics #Transition state theory #cond-mat.mes-hall #cond-mat.stat-mech

paper · pdf · doi:10.1088/0953-8984/22/3/035101

published as 2010 J. Phys.: Condens. Matter 22 035101 · 13 pages, 8 figures, to appear in J. Phys. : Cond. Matt

arxiv created 2009/11/17 · openalex publication_date 2009/12/16 · arxiv updated 2010/04/27 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

The equilibrium density distribution and thermodynamic properties of a Lennard-Jones fluid confined to nanosized spherical cavities at a constant chemical potential was determined using Monte Carlo simulations. The results describe both a single cavity with semi-permeable walls as well as a collection of closed cavities formed at the 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.

Citations

• 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
• The nature of the liquid-vapour interface and other topics in the statistical mechanics of non-uniform, classical fluids
• Density functional theory of inhomogeneous liquids. II. A fundamental measure approach
• Calculations of canonical averages from the grand canonical ensemble
• Perturbation Theory and Equation of State for Fluids. II. A Successful Theory of Liquids

Cited by

• Density functional theory of inhomogeneous liquids. IV. Squared-gradient approximation and classical nucleation theory