Ionic liquids at the air/water interface

Abstract

We present molecular dynamics experiments of Langmuir monolayers of iodide and chloride salts of 1-octyl-3-methylimidazolium adsorbed at water/air interfaces, covering a concentration range that spans from a dilute regime up to the experimental surface saturation for both systems. For the chloride case we observed a propensity to form monolayers with nearly equal surface concentration of both cations and anions; whereas for the iodide system, the more marked propensity to surface solvation of the anionic species leads to the appearance of quasi-double-layered structures. At the surface, the imidazolium rings remain in contact with the aqueous substrate, with a wide variety of orientations with respect to the surface normal direction. Theglobal tilt of the hydrophobic tail of the cations was found to be θtl~40°and 50°, for the chloride and iodide salts, respectively. Polarization fluctuations of the interface are analyzed in terms of those describing charge distributions of the adsorbed species and the electrical response of the solvent as well. The characteristics of the local densities for the ionic species at the interface provide arguments for the microscopic interpretation of the differences observed in scattering experiments on the dependence of the surface tension with the surfactant concentration.