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

James F. Lutsko, "Density functional theory of inhomogeneous liquids. III. Liquid-vapor nucleation", J. of Chemical Physics, 129, 244501 (2008) http://jimlutsko.github.io/files/Lutsko_JCP_2008_3.pdf


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.