Observation of Electrostatically Driven Surface Adsorption in Mixed Surfactant Systems

We employed heterodyne-detected vibrational sum-frequency generation (HD-VSFG) spectroscopy to obtain a molecular-level understanding of the interaction between the anionic surfactant sodium dodecyl ammonium sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). We observed that these surfactants show a strong cooperative effect on their adsorption to the water–air interface. Even at bulk concentrations 1000 times lower than the critical micelle concentrations of SDS and DTAB, a nearly complete surface surfactant layer is observed when both surfactants are present. This strong enhancement of the surface concentrations of DS– and DTA+ can be quantitatively explained from the favorable Coulomb interaction of the oppositely charged headgroups of DS– and DTA+ and the electrostatic interactions with their counterions. The HD-VSFG results are complemented by a modified Langmuir adsorption model in which we include the free energy associated with the electrostatic interactions of the surfactant ions and their counterions.