Complex Coacervation in Asymmetric Solutions of Polycation and Polyanion

We study coacervation upon mixing two aqueous solutions of polyelectrolytes (PEs) with opposite charge, by considering asymmetric effects of PE composition and charge valency. The phase behavior, interfacial structure, and coacervate composition are investigated by a classical density-functional theory. We find two types of coacervation that are different in their density. Supernatant phase in low-density coacervation (LDCA) fully consists of small ions, while in high-density coacervation (HDCA) it contains a considerable amount of PE chains. Asymmetric PE composition could generate an electric double layer at the interface of coacervate. For HDCA, ion density changes monotonically, while for LDCA it shows a global minimum at the double layer, giving a low tension value. Charged species of high charge valency enhance the existence of double layer. Our results explained the coacervate structure of low interfacial tension, which is important for experiments and industrial applications.