title: Density-functional theory and Monte Carlo simulations of the phase behavior of a simple model liquid crystal.
abstract: We consider the phase behavior of a simple model of a liquid crystal by means of modified mean-field density-functional theory (MMF DFT) and Monte Carlo simulations in the grand canonical ensemble (GCEMC). The pairwise additive interactions between liquid-crystal molecules are modeled via a Lennard-Jones potential in which the attractive contribution depends on the orientation of the molecules. We derive the form of this orientation dependence through an expansion in terms of rotational invariants. Our MMF DFT predicts two topologically different phase diagrams. At weak to intermediate coupling of the orientation dependent attraction, there is a discontinuous isotropic-nematic liquid-liquid phase transition in addition to the gas-isotropic liquid one. In the limit of strong coupling, the gas-isotropic liquid critical point is suppressed in favor of a fluid- (gas- or isotropic-) nematic phase transition which is always discontinuous. By considering three representative isotherms in parallel GCEMC simulations, we confirm the general topology of the phase diagram predicted by MMF DFT at intermediate coupling strength. From the combined MMF DFT-GCEMC approach, we conclude that the isotropic-nematic phase transition is very weakly first order, thus confirming earlier computer simulation results for the same model [see M. Greschek and M. Schoen, Phys. Rev. E 83, 011704 (2011)].
authors.affiliation: Stranski-Laboratorium für Physikalische und Theoretische Chemie, Fakultät für Mathematik und Naturwissenschaften, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany.
authors.forename: Stefano
authors.initials: S
authors.lastname: Giura
authors.affiliation: Stranski-Laboratorium für Physikalische und Theoretische Chemie, Fakultät für Mathematik und Naturwissenschaften, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany and Department of Chemical and Biomolecular Engineering, Engineering Building I, Box 7905, North Carolina State University, 911 Partners Way, Raleigh, North Carolina 27695, USA.
authors.forename: Martin
authors.initials: M
authors.lastname: Schoen
mesh_terms: D003198:Computer Simulation; D005740:Gases / Q000737:chemistry; D050866:Liquid Crystals / Q000737:chemistry*; D008956:Models, Chemical; D009010:Monte Carlo Method; D044367:Phase Transition; D013696:Temperature
chemical_list: D005740:Gases