Phase diagram of octapod-shaped nanocrystals in a quasi-two-dimensional planar geometry

Recently, we reported the formation of crystalline monolayers consisting of octapod-shaped nanocrystals (so-called octapods) that had arranged in a square-lattice geometry through drop deposition and fast evaporation on a substrate [W. Qi, J. de Graaf, F. Qiao, S. Marras, L. Manna, and M. Dijkstra, Nano Lett. 12, 5299 (2012)]. In this paper we give a more in-depth exposition on the Monte Carlo simulations in a quasi-two-dimensional (quasi-2D) geometry, by which we modelled the experimentally observed crystal structure formation. Using a simulation model for the octapods consisting of four hard interpenetrating spherocylinders, we considered the effect of the pod length-to-diameter ratio on the phase behavior and we constructed the full phase diagram. The methods we applied to establish the nature of the phase transitions between the various phases are discussed in detail. We also considered the possible existence of a Kosterlitz-Thouless-type phase transition between the isotropic liquid and hexagonal rotator phase for certain pod length-to-diameter ratios. Our methods may prove instrumental in guiding future simulation studies of similar anisotropic nanoparticles in confined geometries and monolayers.