Phase behaviour of mixtures of charged soft disks and spheres

Abstract

We have investigated the phase behaviour of mixtures of soft disks (Gay-Berne oblate ellipsoids, GB) and soft spheres (Lennard-Jones, LJ) with opposite charge as a model of ionic liquid crystals and colloidal suspensions. We have used constant volume Molecular Dynamics simulations and fixed the stoichiometry of the mixture in order to have electroneutrality; three systems have been selected GB : LJ = 1 : 2, GB : LJ = 1 : 1 and GB : LJ = 2 : 1. For each system we have selected three values of the scaled point charge q* of the GB particles, namely 0.5, 1.0 and 2.0 (and a corresponding negative scaled charge of the LJ particles that depends on the stoichiometric ratio). We have found a very rich mesomorphism with the formation, as a function of the scaled temperature, of the isotropic phase, the discotic nematic phase, the hexagonal columnar phase and crystal phases. While the structure of the high temperature phases was similar in all systems, the hexagonal columnar phases exhibited a highly variable morphology depending on the scaled charge and stoichiometry. On the one hand, GB : LJ = 1 : 2 systems form lamellar structures, akin to smectic phases, with an alternation of layers of disks (exhibiting an hexagonal columnar phase) and layers of LJ particles (in the isotropic phase). On the other hand, for the 2 : 1 stoichiometry we observe the formation of a frustrated hexagonal columnar phase with an alternating tilt direction of the molecular axis. We rationalize these findings based on the structure of the neutral ion pair dominating the behaviour at low temperature and high charge.