Solvation Force and Confinement-Induced Phase Transitions of Model Ultra Thin Films

Abstract

The static (equilibrium) properties of atomically thin films confined between two surfaces are studied as a function of surface separation by Grand Canonical Monte Carlo and Molecular Dynamics simulations. A model was used, in which the fluid and wall species consist of two different Lennard-Jones rare gas atoms. This was designed to mimic the static SFA experiments in which it is known that epitaxy is not necessary for inducing an oscillatory solvation force in simple non polar liquids. We have been able to simulate, using this simple system, many aspects of the equilibrium properties observed in the experiments. The solvation force is an exponentially damped, periodic curve. All peaks of maximum amplitude in the solvation force correspond to solid-like structures. These structures melt in increasing the surface separation. A further increase in separation leads to the addition of a whole layer and the recrystallisation of the film. In addition this model displays an interesting phenomenon of confinement induced solid-solid phase transition. Two different stable packing (bcc and triclinic) can be observed in the bilayer film and a transition from one to the other occurs when the surface separation is changed. This phase change has been studied as a function of pressure and temperature. As compared to the simulations using a ‘commensurate’ model, in which the fluid and wall species are made of like atoms, the results obtained here are in much better agreement with experimental findings.

Key Words:

• Thin films
• grand canonical Monte Carlo
• molecular dynamics
• surface force experiments