Distinctive dielectric properties of nematic liquid crystal dimers

We provide an overview of the effect of the molecular structure on the dielectric properties of dimers exhibiting nematic and twist-bend nematic phases with special focus on how the conformational distribution changes are reflected by the dielectric behaviour. Nematic dimers show distinctive dielectric properties which differ from those of archetypical nematic liquid crystals, as for example, unusual temperature dependence of the static permittivity or dielectric spectra characterised by two low-frequency relaxation processes with correlated strengths. The interpretation of such characteristic behaviour requires that account is taken of the effect of molecular flexibility on the energetically favoured molecular shapes. The anisotropic nematic interactions greatly influence the conformational distribution. Dielectric behaviour can be used to track those conformational changes due to dependence of the averaged molecular dipole moment on the averaged molecular shape. Results for a number of dimers are compared and analysed on the basis of the influence of details of the molecular structure, using a recently developed theory for the dielectric properties of dimers.Postprint (author's final draft

Cluster Monte Carlo Simulations of the Nematic--Isotropic Transition

We report the results of simulations of the Lebwohl-Lasher model of the nematic-isotropic transition using a new cluster Monte Carlo algorithm. The algorithm is a modification of the Wolff algorithm for spin systems, and greatly reduces critical slowing down. We calculate the free energy in the neighborhood of the transition for systems up to linear size 70. We find a double well structure with a barrier that grows with increasing system size, obeying finite size scaling for systems of size greater than 35. We thus obtain an estimate of the value of the transition temperature in the thermodynamic limit.Comment: 4 figure

Twist, tilt, and orientational order at the nematic to twist-bend nematic phase transition of 1¿, 9¿-bis(4-cyanobiphenyl-4'-yl) nonane: A dielectric, H 2 NMR, and calorimetric study

The nature of the nematic-nematic phase transition in the liquid crystal dimer 1¿, 9¿-bis(4-cyanobiphenyl-4'-yl) nonane (CB9CB) has been investigated using techniques of calorimetry, dynamic dielectric response measurements, and H2 NMR spectroscopy. The experimental results for CB9CB show that, like the shorter homologue CB7CB, the studied material exhibits a normal nematic phase, which on cooling undergoes a transition to the twist-bend nematic phase (NTB), a uniaxial nematic phase, promoted by the average bent molecular shape, in which the director tilts and precesses describing a conical helix. Modulated differential scanning calorimetry has been used to analyze the nature of the NTB-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and H2 magnetic resonance studies have revealed information on the structural characteristics of the recently discovered twist-bend nematic phase. Analysis of the dynamic dielectric response in both nematic phases has provided an estimate of the conical angle of the heliconical structure for the NTB phase. Capacitance measurements of the electric-field realignment of the director in initially planar aligned cells have yielded values for the splay and bend elastic constants in the high temperature nematic phase. The bend elastic constant is small and decreases with decreasing temperature as the twist-bend phase is approached. This behavior is expected theoretically and has been observed in materials that form the twist-bend nematic phase. H2 NMR measurements characterize the chiral helical twist identified in the twist-bend nematic phase and also allow the determination of the temperature dependence of the conical angle and the orientational order parameter with respect to the director

Molecular dynamics of a binary mixture of twist-bend nematic liquid crystal dimers studied by dielectric spectroscopy

We report a comprehensive dielectric characterization of a liquid crystalline binary mixture composed of the symmetric mesogenic dimer CB7CB and the nonsymmetric mesogenic dimer FFO9OCB. In addition to the high-temperature nematic phase, such a binary mixture shows a twist-bend nematic phase at room temperature which readily vitrifies on slow cooling. Changes in the conformational distribution of the dimers are reflected in the dielectric permittivity and successfully analyzed by means of an appropriate theoretical model. It is shown that the dielectric spectra of the mixture reflect the different molecular dipole properties of the components, resembling in the present case the characteristic dielectric spectra of nonsymmetric dimers. Comparison of the nematic and twist-bend nematic phases reveals that molecular dynamics are similar despite the difference in the molecular environment.Postprint (author's final draft

Miscibility studies of two twist-bend nematic liquid crystal dimers with different average molecular curvatures. A comparison between experimental data and predictions of a Landau mean-field theory for the NTB-N phase transition

We report a calorimetric study of a series of mixtures of two twist-bend liquid crystal dimers, the 1'',7''-bis(4-cyanobiphenyl)-4'-yl heptane (CB7CB) and 1''-(2',4-difluorobiphenyl-4'-yloxy)-9''-(4-cyanobiphenyl-4'-yloxy) nonane (FFO9OCB), the molecules of which have different effective molecular curvatures. High-resolution heat capacity measurements in the vicinity of the NTB-N phase transition for a selected number of binary mixtures clearly indicate a first order NTB-N phase transition for all the investigated mixtures, the strength of which decreases when the nematic range increases. Published theories predict a second order NTB-N phase transition, but we have developed a self-consistent mean field Landau model using two key order parameters: A symmetric and traceless tensor for the orientational order and a short-range vector field which is orthogonal to the helix axis and rotates around of the heliconical structure with an extremely short periodicity. The theory, in its simplified form, depends on two effective elastic constants and explains satisfactorily our heat capacity measurements and also predicts a first-order NTB-N phase transition. In addition, as a complementary source of experimental measurements, the splay (K1) and bend (K3) elastic constants in the conventional nematic phase for the pure compounds and some selected mixtures have been determined.Postprint (author's final draft

Defect configurations and dynamical behavior in a Gay-Berne nematic emulsion

To model a nematic emulsion consisting of a surfactant-coated water droplet dispersed in a nematic host, we performed a molecular dynamics simulation of a droplet immersed in a system of 2048 Gay-Berne ellipsoids in a nematic phase. Strong radial anchoring at the surface of the droplet induced a Saturn ring defect configuration, consistent with theoretical predictions for very small droplets. A surface ring configuration was observed for lower radial anchoring strengths, and a pair of point defects was found near the poles of the droplet for tangential anchoring. We also simulated the falling ball experiment and measured the drag force anisotropy, in the presence of strong radial anchoring as well as zero anchoring strength.Comment: 17 pages, 15 figure

Fish Spawning Aggregations: Where Well-Placed Management Actions Can Yield Big Benefits for Fisheries and Conservation

Marine ecosystem management has traditionally been divided between fisheries management and biodiversity conservation approaches, and the merging of these disparate agendas has proven difficult. Here, we offer a pathway that can unite fishers, scientists, resource managers and conservationists towards a single vision for some areas of the ocean where small investments in management can offer disproportionately large benefits to fisheries and biodiversity conservation. Specifically, we provide a series of evidenced-based arguments that support an urgent need to recognize fish spawning aggregations (FSAs) as a focal point for fisheries management and conservation on a global scale, with a particular emphasis placed on the protection of multispecies FSA sites. We illustrate that these sites serve as productivity hotspots - small areas of the ocean that are dictated by the interactions between physical forces and geomorphology, attract multiple species to reproduce in large numbers and support food web dynamics, ecosystem health and robust fisheries. FSAs are comparable in vulnerability, importance and magnificence to breeding aggregations of seabirds, sea turtles and whales yet they receive insufficient attention and are declining worldwide. Numerous case-studies confirm that protected aggregations do recover to benefit fisheries through increases in fish biomass, catch rates and larval recruitment at fished sites. The small size and spatio-temporal predictability of FSAs allow monitoring, assessment and enforcement to be scaled down while benefits of protection scale up to entire populations. Fishers intuitively understand the linkages between protecting FSAs and healthy fisheries and thus tend to support their protection

Twist, tilt, and orientational order at the nematic to twist-bend nematic phase transition of 1 '',9 ''-bis(4-cyanobiphenyl-4 '-yl) nonane: A dielectric, H-2 NMR, and calorimetric study

The nature of the nematic-nematic phase transition in the liquid crystal dimer 1 '',9 ''-bis(4-cyanobiphenyl-4'-yl) nonane (CB9CB) has been investigated using techniques of calorimetry, dynamic dielectric response measurements, and H-2 NMR spectroscopy. The experimental results for CB9CB show that, like the shorter homologue CB7CB, the studied material exhibits a normal nematic phase, which on cooling undergoes a transition to the twist-bend nematic phase (N-TB), a uniaxial nematic phase, promoted by the average bent molecular shape, in which the director tilts and precesses describing a conical helix. Modulated differential scanning calorimetry has been used to analyze the nature of the N-TB-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and H-2 magnetic resonance studies have revealed information on the structural characteristics of the recently discovered twist-bend nematic phase. Analysis of the dynamic dielectric response in both nematic phases has provided an estimate of the conical angle of the heliconical structure for the N-TB phase. Capacitance measurements of the electric-field realignment of the director in initially planar aligned cells have yielded values for the splay and bend elastic constants in the high temperature nematic phase. The bend elastic constant is small and decreases with decreasing temperature as the twist-bend phase is approached. This behavior is expected theoretically and has been observed in materials that form the twist-bend nematic phase. H-2 NMR measurements characterize the chiral helical twist identified in the twist-bend nematic phase and also allow the determination of the temperature dependence of the conical angle and the orientational order parameter with respect to the director.Postprint (author's final draft

Molecular simulation of chevrons in confined smectic liquid crystals

Chevron structures adopted by confined smectic liquid crystals are investigated via molecular dynamics simulations of the Gay-Berne model. The chevrons are formed by quenching nematic films confined between aligning planar substrates whose easy axes have opposing azimuthal components. When the substrates are perfectly smooth, the chevron formed migrates rapidly towards one of the confining walls to yield a tilted layer structure. However, when substrate roughness is included, by introducing a small-amplitude modulation to the particle- substrate interaction well-depth, a symmetric chevron is formed which remains stable over sufficiently long runtimes for detailed structural information, such as the relevant order parameters and director orien- tation, to be determined. For both smooth and rough boundaries, the smectic order parameter remains non-zero across the entire chevron, implying that layer identity is maintained across the chevron tip. Also, when the surface-stabilised chevron does eventually revert to a tilted layer structure, it does so via surface slippage, such that layer integrity is maintained throughout the chevron to tilted layer relaxation process. </p