Density Functional Theory of Inhomogeneous Liquids: III. Liquid-Vapor Nucleation

TL;DR

This paper uses a novel density functional theory approach with the nudged elastic-band method to analyze vapor bubble and liquid droplet nucleation, providing detailed insights into cluster properties and challenging previous spinodal instability assumptions.

Contribution

It introduces an unbiased method to calculate nucleation pathways and cluster properties, advancing understanding of nucleation processes in Lennard-Jones fluids.

Findings

Nucleation proceeds smoothly rather than via spinodal-like instabilities.

Results agree well with simulations for Lennard-Jones fluids.

Method allows detailed analysis of sub- and super-critical clusters.

Abstract

The process of nucleation of vapor bubbles from a superheated liquid and of liquid droplets from a supersaturated vapor is investigated using the Modified-Core van der Waals model Density Functional Theory (Lutsko, JCP 128, 184711 (2008)). A novel approach is developed whereby nucleation is viewed as a transition from a metastable state to a stable state via the minimum free energy path which is identified using the nudged elastic-band method for exploring free energy surfaces. This allows for the unbiased calculation of the properties of sub- and super-critical clusters, as well as of the critical cluster. For Lennard-Jones fluids, the results compare well to simulation and support the view that even at high supersaturation nucleation proceeds smoothly rather than via spinodal-like instabilities as has been suggested recently.