Two Types of Water at the Water–Surfactant Interface Revealed by Time-Resolved Vibrational Spectroscopy

The surfactant sodium dodecyl sulfate (SDS) is widely used as a detergent for both domestic and industrial applications. It forms a self-assembled monolayer on the surface of water. We report a microscopic model for the interaction between the surfactant and water and between water molecules at the interface, revealed using static and time-resolved two-dimensional sum frequency generation spectroscopy. Two distinct subensembles of water in the presence of this negatively charged SDS surfactant have been identified: those close to the SDS headgroup having fairly isolated O-H groups, i.e., localized O-H stretch vibrations, and those whose O-H stretch vibrations are delocalized, i.e., shared between multiple O-H bonds. The two subensembles are coupled, with subpicosecond energy transfer occurring between them. This is markedly different from O-H bonds at the air-water interface, which are less heterogeneous, and indicates that the water molecules that interact with the surfactant headgroups have hydrogen-bonding properties different from those of water molecules interacting with the other water molecules.