Inconsistency of the density-functional theory of adsorption when using computer simulations

Solvation forces between molecularly rough surfaces

“…The oscillating behavior of fluid density and solvation pressure in thin layers was confirmed in various thermodynamic models and molecular simulations performed assuming ideal ''mathematically'' smooth solid surfaces [14][15][16][17]. This traditional approach stems from the Gibbs definition of dividing solid-fluid interfaces, which provides zero excess of solid density [18].…”

Wetting and drying transitions in mean-field theory: Describing the surface parameters for the theory of Nakanishi and Fisher in terms of a microscopic model

“…24,25 It is unfit to describe the phenomenon of surface layering 26 that is present in integral theories 27 and which also has been observed in Monte Carlo simulations. 28 Furthermore, the square-gradient model always leads to a zero density at a hard wall, which is inconsistent with the wall theorem. 22,29 However, the squaregradient model does have the advantage of being simple enough to be able to unambiguously determine the order of the wetting and drying transitions-something that may be difficult to achieve in more sophisticated density functional theories-thus allowing for a direct test of our microscopic expressions for h 1 and g by making the comparison with the theory of Nakanishi and Fisher.…”

Linear and non-linear theories of solvation forces in fluids

“…In order to implement this theory it is necessary to add an assumption concerning the dependence of the direct correlation function on density for the non-uniform fluid. A comparison with results obtained by computer simulation [10] suggests that the particular assumption made by Saam and Ebner gives erroneous results when applied to physical adsorption problems.…”

“…The required extremal p(r) satisfies equation (10). The effect of solid particles placed in a fluid is to exclude the fluid from the region of the solids.…”