Monte Carlo study of liquid crystal phases of hard and soft spherocylinders

Abstract

We report on a Monte Carlo study of the liquid crystal phases of two model fluids of linear elongated molecules: ~a! hard spherocylinders with an attractive square-well ~SWSC! and ~b! purely repulsive soft spherocylinders ~SRS!, in both cases for a length-to-breadth ratio L*55. Monte Carlo simulations in the isothermal–isobaric ensemble have been performed at a reduced temperature T*55 probing thermodynamic states within the isotropic ~I!, nematic ~N!, and smectic A ~Sm A! regions exhibited by each of the models. In addition, the performance of an entropy criterion to allocate liquid crystalline phase boundaries, recently proposed for the isotropic–nematic transition of the hard spherocylinder ~HSC! fluid, is successfully tested for the SWSC and the SRS fluids and furthermore extended to the study of the nematic–smectic transition. With respect to the more extensively studied HSC fluid, the introduction of the attractive square well in the SWSC model brings the I–N and N–Sm A transitions to higher pressures and densities. Moreover, the soft repulsive core of the SRS fluid induces a similar but quite more significant shift of both of these phase boundaries toward higher densities. This latter effect is apparently in contrast with very recent studies of the SRS fluid at lower temperatures, but this discrepancy can be traced back to the different effective size of the molecular repulsive core at different temperatures.