A perspective on the interfacial properties of nanoscopic liquid drops

Abstract

The structural and interfacial properties of a nanoscopic liquid drops are assessed by means of mechanical, thermodynamical, and statistical mechanical approaches that are discussed in detail, including original developments at both the macroscopic level and the microscopic level of density functional theory (DFT). We emphasize that any approach, such as classical nucleation theory, which is based on a purely macroscopic viewpoint does not lead to a reliable representation when the radius of the drop becomes microscopic. The so-called mechanical route which corresponds to a molecular-level extension of the macroscopic theory of elasticity, and is particularly popular in molecular dynamics simulation, also appears to be unreliable due to the inherent ambiguity in the definition of the microscopic pressure tensor, an observation which has been known for decades but is frequently ignored. In this vein, we propose a non-local mean-field DFT for Lennard-Jones (LJ) fluids to examine drops of varying size. A comparison of the predictions of our DFT with the recent simulation data based on a second-order fluctuation analysis [J. G. Sampayo et al., JCP 132, 141101 (2010)] reveals the consistency of the two treatments. This observation points out the significance of fluctuation effects in small drops, in contrast to what one observes in the case of planar interfaces which are governed by the laws of mechanical equilibrium. A small negative Tolman length and a non-monotonic behaviour of the surface tension with the drop radius are predicted for the LJ fluid. Finally, the limits of a validity of the Tolman approach, the effect of the range of the intermolecular potential, and the behaviour of bubbles are briefly discussed.