Monolayer of aerosol-OT surfactants adsorbed at the air/water interface: An atomistic computer simulation study

An atomistic molecular dynamics (MD) simulation has been carried out to investigate the structural and dynamical properties of a monolayer of the anionic surfactant sodium bis(2-ethyl-1-hexyl) sulfosuccinate (aerosol-OT or AOT) adsorbed at the air/water interface. The simulation is performed at room temperature and at a surface coverage corresponding to that at its critical micelle concentration (78 A(2)/Molecule). The estimated thickness of the adsorbed layer is in good agreement with neutron reflection data. The study shows that the surfactants exhibit diffusive motion in the plane of the interface. It is observed that the surfactant monolayer has a strong influence in restricting both the translational and reorientational motions of the water molecules close to the interface. A drastic difference in the dipolar reorientational motion of water molecules in the aqueous layer is observed with a small variation of the distance from the surfactant headgroups. It has been observed that the water molecules in the first hydration layer (region 1) form strong hydrogen bonds with surfactant headgoups. This results in the slower structural relaxation of water-water hydrogen bonds in the first hydration layer compared to that in the pure bulk water. Most interestingly, we notice that the water molecules present in the layer immediately after the first hydration layer form weaker hydrogen bonds and thus relax faster than even pure bulk water.