Phase transitions of semiflexible hard-sphere chain liquids

We present a density-functional theory for describing liquid-crystalline phase transitions in a fluid of semiflexible hard-sphere chain molecules based on the Onsager second-virial approximation for the free energy. Key ingredients of this theory are the generation of semiflexible chain conformations and calculation of the pair excluded volume and excluded area using a single-chain Monte Carlo enumeration method. First, we investigate the isotropic-nematic phase transition. Next, the theory is extended to account for a smectic-A phase by a bifurcation analysis around the nematic solution. The perturbation is calculated using a lowest-order Fourier series representation.