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Vapour-to-Liquid Nucleation in Associating Lennard-Jones Fluids with Multiple Association Sites

The excess Helmholtz free energy functional for associating Lennard-Jones (LJ) fluid is formulated in terms of a weighted density approximation for short-ranged interactions and a Weeks–Chandler–Andersen approximation for long-range attraction. Within the framework of density functional theory, phase equilibria, vapour–liquid surface tension and vapour–liquid nucleation properties including the density profile, work of formation, excess number of particles and critical supersaturation are investigated for associating LJ fluids with different numbers of association sites (M = 1,2,3,4) per particle. The influences of association energy and association sites on phase equilibria, surface tension and vapour-liquid nucleation properties are discussed.