Numerical study of the phase behavior of rodlike colloids with attractive interactions

Abstract

We examine the influence of attractive interactions on the phase behavior of rodlike colloids. We model the rodlike particles by spherocylinders, for which the phase diagram, in the absence of attraction, is known for arbitrary aspect ratio. We consider the case that the attraction is due to depletion forces caused by the addition of nonadsorbing polymer. The range of this attraction is determined by the size of the polymer. If the radius of gyration of the polymer is small compared to the diameter of the rods, we can model the polymer-induced attraction by a suitable generalization of the square-well model for spherical particles. However, for longer ranged attractions, pairwise additive attractions lead to phase behavior that is very different from what is found when the nonadditivity of depletion forces is taken into account. In our simulations, we find evidence for demixing transitions in the isotropic, nematic and solid phases. We compare our simulation results with predictions based on the perturbation theory of Lekkerkerker and Stroobants [Nuovo Cimento D 16, 949 (1994)]. A crucial input in this theory is the so-called free-volume fraction of the hard spherocylinder reference system. In the work of Lekkerkerker and Stroobants, this quantity is estimated using scaled-particle theory. We test the validity of this approach by comparing it to numerical results for the free-volume fraction.