Solvation force, structure and thermodynamics of fluids confined in geometrically rough pores

The effect of periodic surface roughness on the behavior of confined soft sphere fluids is investigated using grand canonical Monte Carlo simulations. Rough pores are constructed by taking the prototypical slit-shaped pore and introducing unidirectional sinusoidal undulations on one wall. For the above geometry our study reveals that the solvation force response can be phase shifted in a controlled manner by varying the amplitude of roughness. At a fixed amplitude of roughness, a, the solvation force for pores with structured walls was relatively insensitive to the wavelength of the undulation, lambda for 2.3<lambda/sigma(ff)<7, where sigma(ff) is the Lennard-Jones diameter of the confined fluid. This was not the case for smooth walled pores, where the solvation force response was found to be sensitive to the wavelength, for lambda/sigma(ff)<7.0 and amplitudes of roughness, a/sigma(ff)greater than or equal to0.5. The predictions of the superposition approximation, where the solvation force response for the rough pores is deduced from the solvation force response of the slit-shaped pores, was in excellent agreement with simulation results for the structured pores and for lambda/sigma(ff)greater than or equal to7 in the case of smooth walled pores. Grand potential computations illustrate that interactions between the walls of the pore can alter the pore width corresponding to the thermodynamically stable state, with wall-wall interactions playing an important role at smaller pore widths and higher amplitudes of roughness. (C) 2004 American Institute of Physics.