We study the excess free energy due to phase coexistence of fluids by Monte Carlo simulations using successive umbrella sampling in finite L×L×L boxes with periodic boundary conditions. Both the vapor-liquid phase coexistence of a simple Lennard-Jones fluid and the coexistence between A-rich and B-rich phases of a symmetric binary (AB) Lennard-Jones mixture are studied, varying the density ρ in the simple fluid or the relative concentration xA of A in the binary mixture, respectively. The character of phase coexistence changes from a spherical droplet (or bubble) of the minority phase (near the coexistence curve) to a cylindrical droplet (or bubble) and finally (in the center of the miscibility gap) to a slablike configuration of two parallel flat interfaces. Extending the analysis of Schrader et al, [Phys. Rev. E79, 061104 (2009)], we extract the surface free energy γ(R) of both spherical and cylindrical droplets and bubbles in the vapor-liquid case and present evidence that for R the leading order (Tolman) correction for droplets has sign opposite to the case of bubbles, consistent with the Tolman length being independent on the sign of curvature. For the symmetric binary mixture, the expected nonexistence of the Tolman length is confirmed. In all cases and for a range of radii R relevant for nucleation theory, γ(R) deviates strongly from γ() which can be accounted for by a term of order γ()/γ(R)1R2. Our results for the simple Lennard-Jones fluid are also compared to results from density functional theory, and we find qualitative agreement in the behavior of γ(R) as well as in the sign and magnitude of the Tolman length.

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