Surface tension of a Lennard-Jones liquid under supersaturation.
A formally exact Kirkwood-Buff virial formula for the surface tension of a supersaturated interface is derived. A modified Gibbs ensemble method is given that allows the creation of interacting supersaturated phases of equal chemical potential, and which enables the Kirkwood-Buff formula to be applied. The methods are tested by Monte Carlo simulation of a supersaturated Lennard-Jones fluid with a planar liquid-vapor interface. The Kirkwood-Buff results for the supersaturated surface tension are found to be in reasonable agreement with new results obtained here using the recently developed, formally exact, ghost interface method, [M. P. Moody and P. Attard, J. Chem. Phys., 2002, 117, 6705]. The surface tension is obtained as a function of supersaturation at four temperatures, and it is found to decrease with increasing supersaturation, and to vanish at the vapor spinodal. The relevance of the present results to the nucleation of droplets in a supersaturated vapor is discussed.
He
Songnian
S
School of Chemistry F11, The University of Sydney, NSW 2006, Australia.
Attard
Phil
P
D000465:Algorithms; D008956:Models, Chemical; D009010:Monte Carlo Method; D013499:Surface Properties; D013500:Surface Tension; D013696:Temperature; D014835:Volatilization; D014867:Water / Q000737:chemistry
D014867:Water