The construction of mixed monolayers containing hydrophobic and hydrophilic components for which the contact angles for three different liquids vary as a highly nonlinear function of the monolayer composition is reported. It is suggested that a prewetting, crystalline-like layer of water, possibly formed from bulk vapor, is present near the hydrophilic surface, because of an enhanced surface chemical potential ("surface field"). As the concentration of the hydrophilic component is lowered, increasing "quenched randomness" in the distribution of surface fields destroys the surface condensed water phase, thus triggering the observed nonlinearity in the contact angles. The microscopic structure of the water molecules adsorbed on an OH surface is revealed by continuum Monte Carlo simulations, with realistic force fields, and the scenario is supported by mean-field calculations on a simplified lattice-gas model. The observed wetting behavior at 30% relative humidity was altered for a relative humidity 52%, as well as when the surface of the monolayer was molecularly roughened by the addition of two CH2 groups to the hydrophobic (CH,-terminated) component of the mixed monolayers. It is suggested that this transitional phenomenon is due to a possible (true or rounded) surface phase transition, due to the formation of a prewetting water layer. This formation is triggered by variations in the quenched distribution of random surface fields.
IntroductionWetting behavior of ordered and random surfaces has generated considerable interest recently,] in particular, the understanding of its relationship to the surface structure at the molecular level. Therefore, polymeric2 and monolayer surfaces, especially those of thiols on gold,) have been intensively investigated as model systems. Modern theories of wetting are based on phase diagrams representing competing ordering between bulk and surface
We use molecular dynamics to study the nucleation of AgBr in water. After first testing our Born–Mayer–Huggins potentials for Ag+ and Br− by looking at bulk AgBr and at AgBr clusters in vacuo, we consider small numbers of Ag+ and Br− ions immersed in water. The system shows the expected qualitative features of nucleation form solution, including a critical cluster size that decreases with increasing concentration. However, we find that for cluster sizes at least as large as Ag18Br18, the most stable cluster is disordered. This is in stark contrast to clusters in vacuo where clusters as small as Ag4Br4 from ordered fragments of the lattice. These results lend some support to the conjecture that nucleation of crystals from solution is a two-stage process with the first stage consisting of the formation of disordered clusters of solute and the second stage involving the nucleation of a crystal from this solute “melt.”
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