Molecular Dynamics Study of a Surfactant-Mediated Decane−Water Interface: Effect of Molecular Architecture of Alkyl Benzene Sulfonate
Seung Soon Jang, Shiang-Tai Lin, Prabal K. Maiti, Mario Blanco, William A. Goddard III, Patrick J. Shuler, Yongchun Tang
Abstract
The effect of molecular architecture of a surfactant, particularly the attachment position of benzene sulfonate on the hexadecane backbone, at the decane−water interface was investigated using atomistic MD simulations. We consider a series of surfactant isomers in the family of alkyl benzene sulfonates, denoted by m-C16, indicating a benzene sulfonate group attached to the mth carbon in a hexadecane backbone. The equilibrated model systems showed a well-defined interface between the decane and water phases. We find that surfactant 4-C16 has a more compact packing, in terms of the interfacial area and molecular alignment at the interface, than other surfactants simulated in this study. Furthermore, surfactant 4-C16 leads to the most stable interface by having the lowest interface formation energy. The interfacial thickness is the largest in the case of surfactant 4-C16, with the thickness decreasing when the benzene sulfonate is located farther from the attachment position of 4-C16 (the 4th carbon). The interfacial tension profile was calculated along the direction perpendicular to the interface using the Kirkwood−Buff theory. From the comparison of the interfacial tension obtained from the interfacial tension profile, we found that surfactant 4-C16 induces the lowest interfacial tension and that the interfacial tension increases with decreasing interfacial thickness as a function of the attachment position of benzene sulfonate. Such a relationship between the interfacial thickness and interfacial tension is rationalized in terms of the miscibility of the alkyl tail of surfactant m-C16 with decane by comparing the "effective" length of the alkyl tail with the average end-to-end length of decane. Among the surfactants, the effective length of the 4-C16 alkyl tail (9.53 ± 1.36 Å) was found to be closest to that of decane (9.97 ± 1.03 Å), which is consistent with the results from the density profile and the interfacial tension profile.
Group Members
Jang, S. S., Lin, S., Maiti, P. K., Blanco, M., III, W. A. G., Shuler, P. J., & Tang, Y. (2004). Molecular Dynamics Study of a Surfactant-Mediated Decane−Water Interface: Effect of Molecular Architecture of Alkyl Benzene Sulfonate. *J. Phys. Chem. B*, *108*(32), 12130-12140. https://doi.org/10.1021/jp048773n