Adsorption and Self-Assembly of Surfactants on Metal–Water Interfaces

Modifying properties of metal–water interfaces via adsorption of surfactants has applications in electrochemistry and catalysis. We report molecular simulations of adsorption of surfactant molecules on metal surfaces wherein we systematically vary the strength of hydrophobic interaction between surfactant tails, as well as the size of the surfactants’ polar head group. A surfactant molecule is represented by a linear, bead–spring model with a polar “head” bead and a chain of hydrophobic “tail” beads. A smooth surface, strongly attractive to the polar beads, represents the metal surface. Our main findings are that (1) hydrophobic interactions between adsorbed molecules promote adsorption and self-assembly and (2) the morphology of the adsorbed layer is governed by the geometry of the molecules. When the size of the polar bead is the same as that of the hydrophobic beads, an adsorbed self-assembled monolayer (SAM) is formed. When the polar bead is larger than the hydrophobic beads, cylindrical micelles are formed in the bulk and the adsorbed phase. For the adsorbed SAM, the layer is patchy, with a significant fraction of the molecules adsorbed with their polar beads pointing away from the surface. These results corroborate with experimental observations and provide new insights into the molecular nature of adsorbed layers.