A self-consistent field study of a hydrocarbon droplet at the air-water interface

A molecularly detailed self-consistent field (SCF) approach is applied to describe a sessile hydrocarbon droplet placed at the air-water interface. Predictions of the contact angle for macroscopic droplets follow from using Neumann's equation, wherein the macroscopic interfacial tensions are computed from one-gradient calculations for flat interfaces. A two-gradient cylindrical coordinate system with mirror-like boundary conditions is used to analyse the three dimensional shape of the nano-scale oil droplet at the air-water interface. These small droplets have a finite value of the Laplace pressure and concomitant line tension. It has been calculated that the oil-water and oil-vapour interfacial tensions are curvature dependent and increase slightly with increasing interfacial curvature. In contrast, the line tension tends to decrease with curvature. In all cases there is only a weak influence of the line tension on the droplet shape. We therefore argue that the nano-scale droplets, which are described in the SCF approach, are representative for macroscopic droplets and that the method can be used to efficiently generate accurate information on the spreading of oil droplets at the air-water interface in molecularly more complex situations. As an example, non-ionic surfactants have been included in the system to illustrate how a molecularly more complex situation will change the wetting properties of the sessile drop. This short forecast is aimed to outline and to stress the potential of the method.