Like aggregation from unlike attraction: stripes in symmetric mixtures of cross-attracting hard spheres

• Published in: Physical chemistry chemical physics : PCCP Vol. 25; no. 24; pp. 16227 - 16237
• Main Authors: Munaò, Gianmarco, Costa, Dino, Malescio, Gianpietro, Bomont, Jean-Marc, Prestipino, Santi
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 21.06.2023
• Subjects: Attraction; Binary mixtures; Colloiding; Mathematical models; Photonic crystals; Self-assembly; Solid phases
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d3cp01026k

Self-assembly of colloidal particles into striped phases is at once a process of relevant technological interest-just think about the possibility to realise photonic crystals with a dielectric structure modulated along a specific direction-and a challenging task, since striped patterns emerge in a variety of conditions, suggesting that the connection between the onset of stripes and the shape of the intermolecular potential is yet to be fully unravelled. Hereby, we devise an elementary mechanism for the formation of stripes in a basic model consisting of a symmetric binary mixture of hard spheres that interact via a square-well cross attraction. Such a model would mimic a colloid in which the interspecies affinity is of longer range and significantly stronger than the intraspecies interaction. For attraction ranges shorter enough than the particle size the mixture behaves like a compositionally-disordered simple fluid. Instead, for wider square-wells, we document by numerical simulations the existence of striped patterns in the solid phase, where layers of particles of one species are interspersed with layers of the other species; increasing the attraction range stabilises the stripes further, in that they also appear in the bulk liquid and become thicker in the crystal. Our results lead to the counterintuitive conclusion that a flat and sufficiently long-ranged unlike attraction promotes the aggregation of like particles into stripes. This finding opens a novel way for the synthesis of colloidal particles with interactions tailored at the development of stripe-modulated structures. Introducing a flat and sufficiently long-ranged cross attraction in an equimolar mixture of identical hard spheres induces the spontaneous formation of stripes, the longer the attraction range, the thicker the stripes.