Amphiphilic Dimers at Liquid-Liquid Interfaces: A Density Functional Approach

We apply density functional theory to study the structure of dimers at the interface between two partially miscible symmetric liquids. The dimers are built of two tangentially jointed spheres and do not solve the coexisting liquids. The interactions in the system are modeled using Lennard-Jones potentials with different interactions between segments of the dimers and the liquid components. We study how asymmetry of the interactions between dimers and molecules of the liquid, i.e., the degree of dimer amphiphilicity, influences the interfacial structure. Two unexpected phenomena have been found. First, for some systems, the liquid–liquid interface is able to accommodate only a finite amount of dimers. If the amount of added dimers is larger than a threshold value, a part or all of the dimers move to the interior one of the coexisting phase, forming an insoluble sheet inside it, or the initial interface splits into separate parts. The second is a peculiar behavior of the dependence of the interfacial width ...