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Molecular dynamics of thermotropic liquid crystals: Anomalous relaxation dynamics of calamitic and discotic liquid crystals

ABSTRACT

Recent optical kerr effect (OKE) studies have demonstrated that orientational relaxation of rod-like nematogens exhibits temporal power law decay at intermediate times not only near the isotropic–nematic (I–N) phase boundary but also in the nematic phase. Such behaviour has drawn an intriguing analogy with supercooled liquids. We have investigated both collective and single-particle orientational dynamics of a family of model system of thermotropic liquid crystals using extensive computer simulations. Several remarkable features of glassy dynamics are on display including non-exponential relaxation, dynamical heterogeneity, and non-Arrhenius temperature dependence of the orientational relaxation time. Over a temperature range near the I–N phase boundary, the system behaves remarkably like a fragile glass-forming liquid. Using proper scaling, we construct the usual relaxation time versus inverse temperature plot and explicitly demonstrate that one can successfully define a density dependent fragility of liquid crystals. The fragility of liquid crystals shows a temperature and density dependence which is remarkably similar to the fragility of glass forming supercooled liquids. Energy landscape analysis of inherent structures shows that the breakdown of the Arrhenius temperature dependence of relaxation rate occurs at a temperature that marks the onset of the growth of the depth of the potential energy minima explored by the system. A model liquid crystal, consisting of disk-like molecules, has also been investigated in molecular dynamics simulations for orientational relaxation along two isobars starting from the high temperature isotropic phase. The isobars have been so chosen that the phase sequence isotropic (I)–nematic (N)–columnar (C) appears upon cooling along one of them and the sequence isotropic (I)–columnar (C) along the other. While the orientational relaxation in the isotropic phase near the I–N phase transition shows a power law decay at short to intermediate times, such power law relaxation is not observed in the isotropic phase near the I–C phase boundary. The origin of the power law decay in the single-particle second-rank orientational time correlation function (OTCF) is traced to the growth of the orientational pair distribution functions near the I–N phase boundary. As the system settles into the nematic phase, the decay of the single-particle second-rank orientational OTCF follows a pattern that is similar to what is observed with calamitic liquid crystals and supercooled molecular liquids.

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    ABSTRACT: Molecular Dynamics simulations were performed for the Gay-Berne discotic fluid parameterized by GB(0.345, 0.2, 1.0, 2.0). The volumetric phase diagram exhibits isotropic (IL), nematic (ND), and two columnar phases characterized by radial distribution functions: the transversal fluid structure varies between a hexagonal columnar (CD) phase (at higher temperatures and pressures) and a rectangular columnar (CO) phase (at lower temperatures and pressures). The slab-wise analysis of fluid dynamics suggests the formation of grain-boundary defects in the CO phase. Longitudinal fluid structure is highly periodic with narrow peaks for the CO phase, suggestive of a near-crystalline (yet diffusive) system, but is only short-ranged for the CD phase. The IL phase does not exhibit anisotropic diffusion. Transversal diffusion is more favorable in the ND phase at all times, but only favorable at short times for the columnar phases. In the columnar phases, a crossover occurs where longitudinal diffusion is favored over transversal diffusion at intermediate-to-long timescales. The anomalous diffusivity is pronounced in both columnar phases, with three identifiable contributions: (a) the rattling of discogens within a transient "interdigitation" cage, (b) the hopping of discogens across columns, and (c) the drifting motion of discogens along the orientation of the director.
    No preview · Article · May 2014 · Soft Matter