The Tolman length delta [TolmanJ. Chem. Phys. 17, 333 (1949)] measures the extent by which the surface tension of a small liquid drop deviates from its planar value. Despite increasing theoretical attention, debate continues on even the sign of Tolman's length for simple liquids. Recent thermodynamic treatments have proposed a relation between the Tolman length and the isothermal compressibility of the liquid at two-phase coexistence, delta approximately -kappa([script-l])sigma. Here, we review the derivation of this relation and show how it is related to earlier thermodynamic expressions. Its applicability is discussed in the context of the squared-gradient model for the liquid-vapor interface. It is found that the relation is semiquantitatively correct for this model unless one is too close to the critical point.

To describe the full spectrum of surface fluctuations of the interface between phase-separated colloid-polymer mixtures from low scattering vector q (classical capillary wave theory) to high q (bulklike fluctuations), one must take account of the interface's bending rigidity. We find that the bending rigidity is negative and that on approach to the critical point it vanishes proportionally to the interfacial tension. Both features are in agreement with Monte Carlo simulations.

The structure and tension of the interface between a fluid and a spherically shaped hard wall are studied theoretically. The authors show the equivalence of different expressions for the surface tension and Tolman length using the squared-gradient model and density functional theory with a nonlocal, integral expression for the interaction between molecules. Even though both these models yield equilibrium density profiles that do not satisfy the wall theorem, they still obey the basic requirement of mechanical equilibrium. The authors trace back the origin of the difference between these two observations to the (lack of) continuity of the cavity function at the hard wall.

The theory of Nakanishi and Fisher ͓Phys. Rev. Lett. 49, 1565 ͑1982͔͒ describes the wetting behavior of a liquid and vapor phase in contact with a substrate in terms of the surface chemical potential h 1 and the surface enhancement parameter g. Using density functional theory, we derive molecular expressions for h 1 and g and compare with earlier expressions derived from Landau lattice mean-field theory. The molecular expressions are applied to compare with results from density functional theory for a square-gradient fluid in a square-well fluid-substrate potential and with molecular dynamics simulations.

The wetting of a phase-separated colloid-polymer mixture in contact with a hard wall is analyzed using free volume theory in a Nakanishi-Fisher-type approach. We present results for the wetting phase diagram for several model approximations. Our analysis is compared with a previous analysis by Aarts [J. Chem. Phys. 120, 1973 (2004)]. We find that there is a crossover from wetting to drying at a threshold value for the colloid-polymer size ratio and that the transitions are close to the critical point and of second order in nature.