Intrinsic Structure of Hydrophobic Surfaces: The Oil-Water Interface

We investigate the water-oil interface using molecular dynamics simulations of realistic models of alkanes and water. The intrinsic density profiles are computed using a methodology that removes the smoothing effect of the capillary waves. We show that at 300 K the intrinsic width of the gap separating the oil and water phases spans little more than one water molecule diameter, and undergoes very weak short-ranged fluctuations, indicating that the water-oil interface is a rigid molecular structure at ambient temperature. Only near the drying transition (above 500 K for dodecane), the gap features uncoupled fluctuations of the oil and water surfaces, as expected in a typical drying structure. We find that the intrinsic structure of water next to the oil phase is remarkably similar to the bare water-vapor interface.