Quantitative Predictions of the Interfacial Tensions of Liquid–Liquid Interfaces through Atomistic and Coarse Grained Models

• Published in: Journal of chemical theory and computation Vol. 10; no. 5; pp. 1887 - 1899
• Main Authors: Neyt, Jean-Claude, Wender, Aurélie, Lachet, Véronique, Ghoufi, Aziz, Malfreyt, Patrice
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 13.05.2014
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/ct500053c

We report molecular simulations of oil–water liquid–liquid interfaces by using atomistic and coarse grained (CG) MARTINI force fields. We also apply the electronic continuum (EC) model to the MARTINI force field for the calculation of the interfacial tension of oil/water-salt systems. In a first step, we propose to calculate the interfacial tensions using thermodynamic and mechanical definitions of hydrocarbon–water interfacial systems modified by the addition of salts and alcohol. We also establish here the order of magnitude of the long-range corrections to the interfacial tension in fluid–fluid interfaces. Whereas the atomistic models are able to reproduce quantitatively the interfacial tension and the coexisting densities of oil–water systems, the coarse-description shows some deviations in the prediction of the interfacial tensions. Nevertheless, the physical features of these liquid–liquid interfaces are well-captured by this CG description. The CG force field offers then a very challenging alternative that will require however a more developed calibration of the parameters on the basis of liquid–liquid properties.