Effects of wetting and anchoring on capillary phenomena in a confined liquid crystal

D. de Las Heras, E. Velasco, and L. Mederos
J. Chem. Phys., 120, 4949, (2004)     DOI: 10.1063/1.1646374
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A fluid of hard spherocylinders of length-to-breadth ratio L/D=5 confined between two identical planar, parallel walls-forming a pore of slit geometry-has been studied using a version of the Onsager density-functional theory. The walls impose an exclusion boundary condition over the particle's centers of mass, while at the same time favoring a particular anchoring at the walls, either parallel or perpendicular to the substrate. We observe the occurrence of a capillary transition, i.e., a phase transition associated with the formation of a nematic film inside the pore at a chemical potential different from μb-the chemical potential at the bulk isotropic-nematic transition. This transition terminates at an Ising-type surface critical point. In line with previous studies based on the macroscopic Kelvin equation and the mesoscopic Landau-de Gennes approach, our microscopic model indicates that the capillary transition is greatly affected by the wetting and anchoring properties of the semi-infinite system, i.e., when the fluid is in contact with a single wall or, equivalently, the walls are at a very large distance. Specifically, in a situation where the walls are preferentially wetted by the nematic phase in the semi-infinite system, one has the standard scenario with the capillary transition taking place at chemical potentials less than μb (capillary nematization transition or capillary ordering transition). By contrast, if the walls tend to orientationally disorder the fluid, the capillary transition may occur at chemical potentials larger than μb, in what may be called a capillary isotrpization transition or capillary disordering transition. Moreover, the anchoring transition that occurs in the semi-infinite system may affect very decisively the confinement properties of the liquid crystal and the capillary transitions may become considerably more complicated.

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