Liquid-crystal patterns of rectangular particles in a square nanocavity

Abstract

Using density-functional theory in the restricted-orientation approximation, we analyse the liquid-crystal patterns and phase behaviour of a fluid of hard rectangular particles confined in a two-dimensional square nanocavity of side length $H$ composed of hard inner walls. Patterning in the cavity is governed by surface-induced order, capillary and frustration effects, and depends on the relative values of particle aspect ratio $\kappa \equiv L/\sigma$, with $L$ the length and $\sigma$ the width of the rectangles ($L\ge \sigma$), and cavity size $H$. Ordering may be very different from bulk ($H\to \infty$) behaviour when $H$ is a few times the particle length $L$ (nanocavity). Bulk and confinement properties are obtained for the cases $\kappa =1$, 3 and 6. In the confined fluid surface-induced frustration leads to four-fold symmetry breaking in all phases (which become two-fold symmetric). Since no director distorsion can arise in our model by construction, frustration in the director orientation is relaxed by the creation of domain walls (where the director changes by $90^{\circ }$); this configuration is necessary to stabilise periodic phases. For $\kappa =1$ the crystal becomes stable with commensuration transitions taking place as $H$ is varied. In the case $\kappa =3$ the commensuration transitions involve columnar phases with different number of columns. Finally, in the case $\kappa =6$, the high-density region of the phase diagram is dominated by commensuration transitions between smectic structures; at lower densities there is a symmetry-breaking isotropic $\to$ nematic transition exhibiting non-monotonic behaviour with cavity size.

31 pages, 15 figures

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• Orientational ordering of confined hard rods: the effect of shape anisotropy on surface ordering and capillary nematization
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• The study of uniaxial-biaxial phase transition of confined hard ellipsoids using density functional theory
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• Phase behaviour and correlations of parallel hard squares: From highly confined to bulk systems
• Hard rectangles near curved hard walls: tuning the sign of the Tolman length
• Dynamical properties of heterogeneous nucleation of parallel hard squares
• Confinement effects on the random sequential adsorption packings of elongated particles in a slit
• Graphoepitaxy for translational and orientational ordering of monolayers of rectangular nanoparticles
• Highly confined mixtures of parallel hard squares: A Density Functional Theory study