Determination of Equilibrium Adsorbed Morphologies of Surfactants at Metal-Water Interfaces Using a Modified Umbrella Sampling-Based Methodology.

Surfactants adsorb to metal-water interfaces in various morphologies, including self-assembled monolayers (SAMs), cylindrical and spherical micelles, or hemimicelles. Current molecular simulation methods are unable to efficiently sample the formation of these morphologies because of the large diffusive/energetic barriers. We introduce a modified umbrella sampling-based methodology that allows sampling of these morphologies from any initial configuration and provides free energy differences between them. Using this methodology, we have studied adsorption behavior of cationic [quaternary ammonium (quat) of 4 and 12 carbon long alkyl tails], uncharged [decanethiol], and anionic [phosphate monoester] surfactants and their mixtures at a gold-water interface. We find that while Coulombic repulsion between the charged head groups of quat-4 limits their adsorption to a sparse layer, stronger hydrophobic interactions between the alkyl tails of quat-12 promote adsorption resulting in a morphology with adsorbed hemispherical micelles sitting atop a monolayer. Decanethiol molecules adsorb in a densely packed bilayer with the molecules standing-up on the surface in the first layer and lying parallel to the surface in the second layer. Cationic and anionic surfactant mixtures display a synergistic adsorption behavior. These results elucidate the role of molecular characteristics in dictating the nature of adsorbed morphologies of surfactants at metal-water interfaces.