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Orientational and positional ordering properties of liquid crystal monolayers are examined by means of Fundamental-Measure Density Functional Theory. Particles forming the monolayer are modeled as hard parallelepipeds of square section of size sigma and length L. Their shapes are controlled by the aspect ratio kappa = L/sigma (>1 for prolate and <1 for oblate shapes). The particle centers of mass are restricted to a flat surface and three possible and mutually perpendicular orientations (in-plane and along the layer normal) of their uniaxial axes are allowed. We find that the structure of the monolayer depends strongly on particle shape and density. In the case of rod-like shapes, particles align along the layer normal in order to achieve the lowest possible occupied area per particle. This phase is a uniaxial nematic even at very low densities. In contrast, for plate-like particles, the lowest occupied area can be achieved by random in-plane ordering in the monolayer, i.e., planar nematic ordering takes place even at vanishing densities. It is found that the random in-plane ordering is not favorable at higher densities and the system undergoes an in-plane ordering transition forming a biaxial nematic phase or crystallizes. For certain values of the aspect ratio, the uniaxial-biaxial nematic phase transition is observed for both rod-like and plate-like shapes. The stability region of the biaxial nematic phase enhances with decreasing aspect ratios for plate-like particles, while the rod-like particles exhibit a reentrant phenomenon, i.e., a sequence of uniaxial-biaxial-uniaxial nematic ordering with increasing density if the aspect ratio is larger than 21.34. In addition to this, packing fraction inversion is observed with increasing surface pressure due to the alignment along the layers normal. At very high densities the nematic phase destabilizes to a nonuniform phases (columnar, smectic, or crystalline phases) for both shapes. ; We gratefully acknowledge illuminating discussions with G. Odriozola. Financial support from Comunidad Autónoma de Madrid (Spain) under the R&D Programme of Activities MODELICO-CM/S2009ESP-1691, and from MINECO (Spain) under Grant Nos. FIS2010-22047-C01 and FIS2010-22047-C04 is acknowledged. S.V. acknowledges the financial support of the Hungarian State and the European Union under the TAMOP-4.2.2.A-11/1/KONV-2012-0071.

The effect of cylindrical confinement on the phase behaviour of a system of parallel hard rods is studied using Onsager's second-virial theory. The hard rods are represented as hard cylinders of diameter D and length L, while the cylindrical pore is infinite with diameter W. The interaction between the wall and the rods is hard repulsive, and it is assumed that molecules are parallel to the surface of the pore (planar anchoring). In very narrow pores (D 100D, results for bulk and confined fluids agree well due to the short range effect of the wall (∼3-4D). ; SV acknowledges the financial support of the Hungarian State and the European Union under the TAMOP-4.2.2.A-11/1/KONV-2012-0071. Financial support from Comunidad Autónoma de Madrid (Spain) under the R&D Programme of Activities MODELICOCM/ S2009ESP-1691, and from MINECO (Spain) under grants FIS2010-22047-C01 and FIS2010-22047-C04 is also acknowledged. ; Publicado