The Role of Surfactant Force Field on the Properties of Liquid/Liquid Interfaces

Surfactant-laden liquid/liquid interfaces mediate numerous chemical processes, from commercial applications of microemulsions to chemical separations. Classical molecular dynamics simulation is a prevalent method for studying microscopic and thermodynamic properties of such interfaces. However, the extent to which these features can be reliably predicted, and the variations in predicted behavior, depend upon the force field parameters employed. At present, the impact of force fields upon simulated properties is relatively understudied. Yet recent advances to sampling and analysis algorithms are increasing the interpretation of simulation data and therefore understanding force field dependence is increasingly relevant. In this study, the impact of the force field of the surfactant tri-n-butyl phosphate (TBP), as well as that of water, is investigated at a water/(n-hexane + surfactant) interface. Empirical charge scaling was employed to modulate the hydrophilicity of the surfactant. As anticipated, the relative hydrophilicity of TBP influences a number of properties, including the adsorbed concentrations of TBP at the interface, and macroscopic properties that result from hydrogen bonding interactions, such as interfacial tension and width. The dynamic properties of solvents at the interface are strongly modulated by the variation in hydrogen bond strength caused by different charge scaling of the TBP model. This includes the residence times of water at the interface, where stronger water-TBP hydrogen bonding causes long-lived residences. Interestingly, there are a number of features that are relatively insensitive to the TBP hydrophilicity. In one important case, the concentration of water-bridged TBP dimers was only impacted for the least hydrophilic model. As these dimeric species are the building block of surface protrusions that lead to water transport across the interface, this implies that collective organizational patterns and surface structures that derive from multiple driving forces (e.g. TBP hydrophilicity and organic solvent free energies of solvation) are less sensitive to individual force field parameters. Further, we note that competitive interactions can "cancel" the effects of changing TBP charge on interfacial properties. One example is the orientation and hydrogen bonding structure of interfacial water, where the direct TBP-water hydrogen bonding competes against the indirect TBP-induced interfacial roughness. In combination, these observations may assist future simulation studies in calibrating surfactant models to, or interpreting results of, a broad range of dynamic, structural and thermodynamic properties.