Interfacial and wetting properties of a binary point Yukawa fluid

Details Interfacial and wetting properties of a binary point Yukawa fluid Interfacial and wetting properties of a binary point Yukawa fluid

2008-10-29

arxiv.org/abs/0810.5229v1

J. Chem. Phys. 129, 214709 (2008).

Physics

Condensed Matter

Soft Condensed Matter

11 pages, 7 figures. Accepted for publication in Journal of Chemical Physics

Scientific paper

10.1063/1.3027515

We investigate the interfacial phase behavior of a binary fluid mixture composed of repulsive point Yukawa particles. Using a simple approximation for the Helmholtz free energy functional, which yields the random phase approximation (RPA) for the pair direct correlation functions, we calculate the equilibrium fluid density profiles of the two species of particles adsorbed at a planar wall. We show that for a particular choice (repulsive exponential) of the wall potentials and the fluid pair-potential parameters, the Euler-Lagrange equations for the equilibrium fluid density profiles may be transformed into a single ordinary differential equation and the profiles obtained by a simple quadrature. For certain other choices of the fluid pair-potential parameters fluid-fluid phase separation of the bulk fluid is observed. We find that when such a mixture is exposed to a planar hard-wall, the fluid exhibits complete wetting on the species 2 poor side of the binodal, i.e. we observe a thick film of fluid rich in species 2 adsorbed at the hard-wall. The thickness of the wetting film grows logarithmically with the concentration difference between the fluid state-point and the binodal and is proportional to the bulk correlation length of the intruding (wetting) fluid phase. However, for state points on the binodal that are further from the critical point, we find there is no thick wetting film. We determine the accompanying line of first-order (pre-wetting) surface phase transitions which separate a thin and thick adsorbed film. We show that for some other choices of repulsive wall potentials the pre-wetting line is still present, but its location and extent in the phase diagram is strongly dependent on the wall-fluid interaction parameters.

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