''Critical clusters'' in a supersaturated vapor: Theory and Monte Carlo simulation

Journal Article · Sat Mar 01 04:00:00 UTC 1980 · J. Stat. Phys.; (United States)

DOI:https://doi.org/10.1007/BF01014648· OSTI ID:5281693

Binder, K; Kalos, M H

A new thermodynamic analysis is given for the equilibrium between a liquid cluster and the surrounding supersaturated gas phase in a finite constant volume. It is shown that for constant total density and intermediate volume this equilibrium is stable, although it is unstable for very large volume. We show that observation of the critical cluster size l* then yields information on the surface free energy of the liquid cluster. THe accuracy of previous approximate prescriptions for obtaining the free energy of physical cluster is investigated. As an application, the theory is used to analyze Monte Carlo simulations of the two-dimensional lattice gas model at low temperatures. We obtain cluster surface area, diffusivity, and free energy for clusters with 26 < or =l< or =500. It is found that the capillarity approximation is inaccurate for l< or =100, but the free energy of small clusters is higher than the result of classical nucleation theory, in contrast to what one expects from Tolman-like corrections. We interpret these results, deriving low-temperature series expansions for very small clusters, thus showing that the capillarity approximation both underestimates the surface energy and overestimates the surface entropy of very small clusters. Finally, we use our results to give a speculative explanation of recent nucleation experiments. The dependence of the cluster diffusivity on cluster size is tentatively explained in terms of a crossover between two mechanisms yielding different power laws.

• Research Organization: IFF, KFA Juelich, Juelich, West Germany
• OSTI ID: 5281693
• Journal Information: J. Stat. Phys.; (United States), Journal Name: J. Stat. Phys.; (United States) Vol. 22:3; ISSN JSTPB
• Country of Publication: United States
• Language: English

Related Subjects

657006* -- Theoretical Physics-- Statistical Physics &amp; Thermodynamics-- (-1987)
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
COMPUTERIZED SIMULATION
ENERGY
EQUILIBRIUM
FLUIDS
FREE ENERGY
GASES
MONTE CARLO METHOD
NUCLEATION
PHYSICAL PROPERTIES
SATURATION
SIMULATION
STABILITY
SUPERSATURATION
SURFACE ENERGY
SURFACE PROPERTIES
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
TWO-DIMENSIONAL CALCULATIONS
VAPORS