Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 17, Issue 9, Pages 6389-6400Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4cp04812a
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Funding
- MINECO (Spain) [FIS2010-22047-C01, FIS2010-22047-C04]
- Hungarian State
- European Union [TAMOP-4.2.A-11/1/KONV-2012-0071]
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We extend our previous work on monolayers of uniaxial particles [J. Chem. Phys., 2014, 140, 204906] to study the effect of particle biaxiality on the phase behavior of liquid-crystal monolayers. Particles are modelled as board-like hard bodies with three different edge lengths sigma(1) >= sigma(2) >= sigma(3), and the restricted-orientation approximation (Zwanzig model) is used. A density-functional formalism based on the fundamental-measure theory is used to calculate phase diagrams for a wide range of values with the largest aspect ratio kappa(1) = sigma(1)/sigma(3) is an element of [1,100]. We find that particle biaxiality in general destabilizes the biaxial nematic phase already present in monolayers of uniaxial particles. While plate-like particles exhibit strong biaxial ordering, rod-like ones with kappa(1) > 21.34 exhibit reentrant uniaxial and biaxial phases. As particle geometry is changed from uniaxial- to increasingly biaxial-rod-like, the region of biaxiality is reduced, eventually ending in a critical-end point. For kappa(1) > 60, a density gap opens up in which the biaxial nematic phase is stable for any particle biaxiality. Regions of the phase diagram, where packing-fraction inversion occurs (i.e. packing fraction is a decreasing function of density), are found. Our results are compared with the recent experimental studies on nematic phases of magnetic nanorods.
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