Columnar phases of discotics with orientation-dependent interactions

Abstract

The liquid crystal phase diagram of fluids of rigid discotics with soft interactions has been investigated by means of Monte Carlo simulations. The particles are modeled by spherocylinders or Gay-Berne ellipsoids with thickness/diameter aspect ratios of L/D=0.2. The study includes a variety of pair interaction potentials, featuring different energetic dependencies on the orientation of the particles. Three distinct types of models are considered: (i) models with a homogeneous interaction around the molecular core, (ii) models favoring stacked pair configurations, and (iii) models favoring edge-to-edge configurations. The stability and internal structure of the isotropic, nematic, and the different hexatic columnar phases exhibited by these fluids are discussed. The results indicate that the spherocylinder and ellipsoidal models differ in fundamental trends of their phase behavior. The spherocylinder fluids display more extended ranges of stability and longer pair correlation lengths in the columnar phases than the ellipsoidal models. As a consequence, as opposed to ellipsoids, the nematic phase for spherocylinders with the title aspect ratio tends to be entropically suppressed, even under favorable energetics.