Spontaneous pattern formation in monolayers of binary mixtures with competing interactions

Soft Matter. 2024 Feb 14;20(7):1410-1424. doi: 10.1039/d3sm01537h.

Abstract

A model for a monolayer of two types of particles spontaneously forming ordered patterns is studied using a mesoscopic theory and MC simulations. We assume hard-cores of the same size a for both components. For r > a, like particles attract and repel each other at short and large distances, respectively, with the same potential u(r) for both species, and the cross-interaction is -u(r). The model is inspired by oppositely charged particles or macromolecules with preferential solubility in different components of a solvent that is close to a miscibility critical point, in particular by inclusions in biological membranes. We obtain the phase diagram in the chemical potentials and temperature variables as well as in the concentration, density and temperature variables, using the mean-field one-shell approximation. We find that the presence of the second component significantly extends the temperature range of stability of the ordered phases. We obtain three stable phases with periodic concentration: the lamellar L phase with alternating stripes of the two components for similar chemical potentials, and a hexagonal arrangement of the clusters of the minority component in the liquid of the majority component. The latter two phases, however, are stable only at relatively high temperatures. At lower temperatures, the L phase coexists with a disordered one-component fluid or with very dilute gas with mixed components. At still lower temperatures, the one-component phase coexisting with the L phase can be disordered or ordered, depending on the chemical potentials. The theoretical results are confirmed by MC simulations for selected thermodynamic states.