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

TL;DR

This study investigates the phase behavior of a Lennard-Jones fluid confined in nano-sized cavities, revealing a reverse liquid-vapor transition where the fluid switches from liquid to vapor as volume decreases, using Monte Carlo simulations and DFT.

Contribution

It provides a detailed comparison between Monte Carlo simulations and classical DFT for confined fluids, highlighting the accuracy of DFT in predicting phase transitions in nano-cavities.

Findings

DFT accurately predicts pressure and structure of confined fluids.

Identification of a reverse liquid-vapor transition at nanoscale confinement.

Both theory and simulation show phase change from liquid to vapor at decreasing volume.

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.