Pattern formation and self-assembly driven by competing interactions

Colloidal fluids interacting via effective potentials which are attractive at the short range and repulsive at the long range have long been raising considerable attention because such an instance provides a simple mechanism leading to pattern formation even for isotropic interactions. If the competition between attraction and repulsion is strong enough, the gas–liquid phase transition is suppressed, and replaced by the formation of mesophases, i.e., inhomogeneous phases displaying periodic density modulations whose length, although being larger than the particle size, cannot nevertheless be considered macroscopic. We describe a fully numerical implementation of density-functional theory in three dimensions, tailored to periodic phases. The results for the equilibrium phase diagram of the model are compared with those already obtained in previous investigations for the present system as well as for other systems which form mesophases. The phase diagram which we find shows a strong similarity with that of block copolymer melts, in which self-assembly also results from frustration of a macroscopic phase separation. As the inhomogeneous region is swept by increasing the density from the low-density side, one encounters clusters, bars, lamellae, inverted bars, and inverted clusters. Moreover, a bicontinuous gyroid phase consisting of two intertwined percolating networks is predicted in a narrow domain between the bar and lamellar phases.