Density functional theory of inhomogeneous liquids. III. Liquid-vapor nucleation

2008/07/25 by James F. Lutsko · 5 citations
Earth and Planetary Sciences · Engineering · Materials Science · Physics and Astronomy · #Phase Equilibria and Thermodynamics #Solidification and crystal growth phenomena #cond-mat.mtrl-sci #cond-mat.soft #cond-mat.stat-mech #nanoparticles nucleation surface interactions

paper · pdf · doi:10.1063/1.3043570

published as J. Chem. Phys. 129, 244501 (2008)

arxiv created 2008/07/25 · openalex publication_date 2008/12/22 · arxiv updated 2009/12/01 · openalex created_date 2016/06/24 · openalex updated_date 2026/07/28

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 [J. F. Lutsko, J. Chem. Phys. 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 at low to moderate supersaturation nucleation proceeds smoothly rather than via spinodal-like instabilities as has been suggested recently. The possibility that the nucleation barrier vanishes at high supersaturation is, however, not ruled out.

Citations

• 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
• Theoretical description of the nucleation of vapor bubbles in a superheated fluid
• Dynamical density functional theory and its application to spinodal decomposition

Cited by

• Nucleation of colloids and macromolecules in a finite volume
• Phase behavior of a confined nanodroplet in the grand-canonical ensemble: the reverse liquid–vapor transition
• Density functional theory of inhomogeneous liquids. IV. Squared-gradient approximation and classical nucleation theory
• Minimum free-energy path of homogenous nucleation from the phase-field equation
• Predictions of homogeneous nucleation rates for n-alkanes accounting for the diffuse phase interface and capillary waves