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

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.

Classical nucleation theory from a dynamical approach to nucleation

“…Indeed, both simulation 3 and Density Functional Theory calculations [4][5][6][7] show, e.g., that a liquid cluster forming in a vapor has a broad and diffuse interface with the surrounding vapor. In fact, for small clusters, all molecules in the cluster could be classified as being part of the interface with no bulk material present at all.…”

Phase separation dynamics in a two-dimensional magnetic mixture

“…The simplest one is CNT, a macroscopic approach, involving the bulk pressure and line tension. The resulting nucleation barriers show familiar behavior (as compared to other model systems 12,48 ) and predicts that the barrier height increases as one approaches to the binodal. In this regime CNT is expected to give a good approximation for c .…”

“…From the positions of the maxima in (N ex ) we also see that typical critical droplets contain between a few ten and a few hundred of particles, consistent with results of other DFT studies. 12,48 Our data for the height of the nucleation barrier as a function of the concentration are summarized in Fig. 8, where we have included the corresponding macroscopic (CNT) results from Fig.…”

“…Of particular interest are the density profiles corresponding to the most likely pathway (MLP) that go up to and then descend from the critical droplet state. 12,[47][48][49] These MLP profiles should correspond to what one would observe experimentally for nucleation in the system.…”

Reaction Path Optimization and Sampling Methods and Their Applications for Rare Events

“…(Brooks et al 2009) Other improved optimizers, (Alfonso & Jordan 2003;Bergonzo et al 2009;Galván & Field 2008) and other software packages, such as AMBER, (Case et al 2005) have efficient implementations of NEB as well. In general, the NEB methods have been applied in numerous studies, including diffusion processes on surfaces, (Ágoston & Albe 2010;Sørensen et al 1996;Uberuaga et al 2000;Villarba & Jonsson 1994;Yang et al 2009) nucleation process, (Lutsko 2008) stability of nanoparticle, (Vélez et al 2008) and dissociative adsorption of a molecule on a surface. (Mills 1995) Xie, Liu and Yang adapted the NEB method for enzymatic reactions.…”