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Understanding the role of the counterion species in surfactant solutions is a complicated task, made harder by the fact that, experimentally, it is not possible to vary independently bulk and surface quantities. Here, we perform molecular dynamics simulations at constant surface coverage of the liquid/vapor interface of lithium, sodium, potassium, rubidium, and cesium dodecyl sulfate aqueous solutions. We investigate the effect of counterion type and charge sign on the surface tension of the solution, analyzing the contribution of different species and moieties to the lateral pressure profile. The observed trends are qualitatively compatible with the Hofmeister series, with the notable exception of sodium. We point out a possible shortcoming of what is at the moment, in our experience, the most realistic nonpolarizable force field (CHARMM36) that includes the parametrization for the whole series of alkali counterions. In the artificial system where the counterion and surfactant charges are inverted in sign, the counterions become considerably harder. This charge inversion changes considerably the surface tension contributions of the counterions, surfactant headgroups, and water molecules, stressing the key role of the hardness of the counterions in this respect. However, the hydration free energy gain of the counterions, occurring upon charge inversion, is compensated by the concomitant free energy loss of the headgroups and water molecules, leading to a negligible change in the surface tension of the entire system.

the journal of physical chemistry b

Contribution of Different Molecules and Moieties to the Surface Tension in Aqueous Surfactant Solutions. II: Role of the Size and Charge Sign of the Counterions