Role of the Counterions in the Surface Tension of Aqueous Surfactant Solutions. A Computer Simulation Study of Alkali Dodecyl Sulfate Systems

We have investigated the surface tension contributions of the counterions, surfactant headgroups and tails, and water molecules in aqueous alkali dodecyl sulfate (DS) solutions close to the saturated surface concentration by analyzing the lateral pressure profile contribution of these components using molecular dynamics simulations. For this purpose, we have used the combination of two popular force fields, namely KBFF for the counterions and GROMOS96 for the surfactant, which are both parameterized for the SPC/E water model. Except for the system containing Na⁺ counterions, the surface tension of the surfactant solutions has turned out to be larger rather than smaller than that of neat water, showing a severe shortcoming of the combination of the two force fields. We have traced back this failure of the potential model combination to the unphysically strong attraction of the KBFF counterions, except for Na⁺, to the anionic head of the surfactants. Despite this failure of the model, we have observed a clear relation between the soft/hard character (in the sense of the Hofmeister series) and the surface tension contribution of the counterions, which, given the above limitations of the model, can only be regarded as an indicative result. We emphasize that the obtained results, although in a twisted way, clearly stress the crucial role the counterions of ionic surfactants play in determining the surface tension of the aqueous surfactant solutions.