Simulation and theory of hybrid aligned liquid crystal films.

We present a study of the effects of nanoconfinement on a system of hard Gaussian overlap particles interacting with planar substrates through the hard-needle-wall potential, extending earlier work by two of us [D. J. Cleaver and P. I. C. Teixeira, Chem. Phys. Lett. 338, 1 (2001)]. Here, we consider the case of hybrid films, where one of the substrates induces strongly homeotropic anchoring, while the other favors either weakly homeotropic or planar anchoring. These systems are investigated using both Monte Carlo simulation and density-functional theory, the latter implemented at the level of Onsager's second-virial approximation with Parsons-Lee rescaling. The orientational structure is found to change either continuously or discontinuously depending on substrate separation, in agreement with earlier predictions by others. The theory is seen to perform well in spite of its simplicity, predicting the positional and orientational structure seen in simulations even for small particle elongations.

Entropy-driven formation of the gyroid cubic phase.

We show, by computer simulation, that tapered or pear-shaped particles, interacting through purely repulsive interactions, can freely self-assemble to form the three-dimensionally periodic, gyroid cubic phase. The Ia3d gyroid cubic phase is formed by these particles on both compression of an isotropic configuration and expansion of a smectic A bilayer arrangement. For the latter case, it is possible to identify the steps by which the topological transformation from nonintersecting planes to fully interpenetrating, periodic networks takes place.

Using particle shape to induce tilted and bistable liquid crystal anchoring.

We use Monte Carlo simulations of hard Gaussian overlap (HGO) particles symmetrically confined in slab geometry to investigate the role of particle-substrate interactions on liquid crystalline anchoring. Despite the restriction here to purely steric interactions and smooth substrates, a range of behaviors are captured, including tilted anchoring and homeotropic-planar bistability. These macroscopic behaviors are all achieved through appropriate tuning of the microscopics of the HGO-substrate interaction, based upon nonadditive descriptions for the HGO-substrate shape parameter.

Computer simulation of a liquid-crystal anchoring transition.

We present a study of the effects of confinement on a system of hard Gaussian overlap particles interacting with planar substrates through the hard-needle-wall potential. Using geometrical arguments to calculate the molecular volume absorbed at the substrates, we show that both planar and homeotropic arrangements can be obtained using this model. Monte Carlo simulations are then used to perform a systematic study of the model's behavior as a function of the system density and the hard-needle-wall interaction parameter. As well as showing the homeotropic to planar anchoring transition, the anchoring phase diagrams computed from these simulations indicate regions of bistability. This bistable behavior is examined further through the explicit simulation of field-induced two-way switching between the two arrangements.

Computer simulations of hard pear-shaped particles.

We report results obtained from Monte Carlo simulations investigating mesophase formation in two model systems of hard pear-shaped particles. The first model considered is a hard variant of the truncated Stone-expansion model previously shown to form nematic and smectic mesophases when embedded within a 12-6 Gay-Berne-like potential [R. Berardi, M. Ricci, and C. Zannoni, ChemPhysChem 7, 443 (2001)]. When stripped of its attractive interactions, however, this system is found to lose its liquid crystalline phases. For particles of length to breadth ratio k=3, glassy behavior is seen at high pressures, whereas for k=5 several bi- layerlike domains are seen, with high intradomain order but little interdomain orientational correlation. For the second model, which uses a parametric shape parameter based on the generalized Gay-Berne formalism, results are presented for particles with elongation k=3, 4, and 5. Here, the systems with k=3 and 4 fail to display orientationally ordered phases, but the system with k=5 shows isotropic, nematic and, unusual for a hard-particle model, interdigitated smectic A2 phases.