Molecular orientational order of nitroxide radicals in liquid crystalline media

The orientational distribution of a set of stable nitroxide radicals in aligned liquid crystals 5CB (nematic) and 8CB (smectic A) was studied in detail by numerical simulation of EPR spectra. The order parameters up to the 10th rank were measured. The directions of the principal orientation axes of the radicals were determined. It was shown that the ordering of the probe molecules is controlled by their interaction with the matrix molecules more than the inherent geometry of the probes themselves. The rigid fused phenanthrene-based (A5) and 2-azaphenalene (A4) nitroxides as well as the rigid core elongated C11 and 5α-cholestane (CLS) nitroxides were found to be most sensitive to the orientation of the liquid crystal matrixes.

Multiple liquid-crystals and NMR

The use of more than one liquid crystal solvents to determine molecular structure and conformation is discussed. Liquid crystals of similar and opposite signs of diamagnetic anisotropies are considered separately since they lead to different novel applications. Advantages of such experiments over those employing single solvents are pointed out with illustrative examples.

NMR spectra of 2-fluoropyridine in nematic liquid crystals

The NMR spectra of 2-fluoropyridine in two nematic liquid crystal solvents have been investigated. The direct dipole-dipole coupling constants thus derived have been used to obtain the structural information. The values of the interproton distance ratios arc found to be similar to those in pyridine. The results indicate negligible anisotropic contributions of lH-l9F indirect couplings.

Static and dynamic properties of incommensurate smectic-AIC liquid crystals

We study the elasticity, topological defects, and hydrodynamics of the recently discovered incommensurate smectic (AIC) phase, characterized by two collinear mass density waves of incommensurate spatial frequency. The low-energy long-wavelength excitations of the system can be described by a displacement field u(x) and a ��phason�� field w(x) associated, respectively, with collective and relative motion of the two constituent density waves. We formulate the elastic free energy in terms of these two variables and find that when w=0, its functional dependence on u is identical to that of a conventional smectic liquid crystal, while when u=0, its functional dependence on w is the same as that for the angle variable in a slightly anisotropic XY model. An arbitrariness in the definition of u and w allows a choice that eliminates all relevant couplings between them in the long-wavelength elastic energy. The topological defects of the system are dislocations with nonzero u and w components. We introduce a two-dimensional Burgers lattice for these dislocations, and compute the interaction between them. This has two parts: one arising from the u field that is short ranged and identical to the interaction between dislocations in an ordinary smectic liquid crystal, and one arising from the w field that is long ranged and identical to the logarithmic interaction between vortices in an XY model. The hydrodynamic modes of the AIC include first- and second-sound modes whose direction-dependent velocities are identical to those in ordinary smectics. The sound attenuations have a different direction dependence, however. The breakdown of hydrodynamics found in conventional smectic liquid crystals, with three of the five viscosities diverging as 1/? at small frequencies ?, occurs in these systems as well and is identical in all its details. In addition, there is a diffusive phason mode, not found in ordinary smectic liquid crystals, that leads to anomalously slow mechanical response analogous to that predicted in quasicrystals, but on a far more experimentally accessible time scale.

Silver nitrate-acetonitrile and iodine-benzene complexes as studied by NMR in thermotropic liquid crystals

Silver nitrate-acetonitrile and π iodine-benzene complexes in thermotropic liquid crystals have been studied by 1H, 2H, and 13C NMR spectroscopy and by optical microscopy. Evidence for at least two silver complexes in each liquid crystal is presented.

Colloidal dispersions in a liquid crystalline medium

We have prepared stable colloidal suspensions in a lyotropic liquid crystal exhibiting an isotropic-nematic-lamellar phase sequence. Small angle neutron scattering (SANS) and dynamic light scattering (DLS) studies show the existence of attractive interparticle interactions in the nematic phase, which lead to a gas-liquid transition of the particles. The resulting liquid phase is weakly anisotropic. Further, the nematic-lamellar transition of the liquid crystal is found to be accompanied by a liquid-solid transition of the particles.

13C-1H HSQC Experiment of Probe Molecules Aligned in Thermotropic Liquid Crystals: Sensitivity and Resolution Enhancement in the Indirect Dimension

The spectra of molecules oriented in liquid crystalline media are dominated by partially averaged dipolar couplings. In the 13C–1H HSQC, due to the inefficient hetero-nuclear dipolar decoupling in the indirect dimension, normally carried out by using a π pulse, there is a considerable loss of resolution. Furthermore, in such strongly orienting media the 1H–1H and 13C–1H dipolar couplings leads to fast dephasing of transverse magnetization causing inefficient polarization transfer and hence the loss of sensitivity in the indirect dimension. In this study we have carried out 13C–1H HSQC experiment with efficient polarization transfer from 1H to 13C for molecules aligned in liquid crystalline media. The homonuclear dipolar decoupling using FFLG during the INEPT transfer delays and also during evolution period combined with the π pulse heteronuclear decoupling in the t1 period has been applied. The studies showed a significant reduction in partially averaged dipolar couplings and thereby enhancement in the resolution and sensitivity in the indirect dimension. This has been demonstrated on pyridazine and pyrimidine oriented in the liquid crystal. The two closely resonating carbons in pyrimidine are better resolved in the present study compared to the earlier work [H.S. Vinay Deepak, Anu Joy, N. Suryaprakash, Determination of natural abundance 15N–1H and 13C–1H dipolar couplings of molecules in a strongly orienting media using two-dimensional inverse experiments, Magn. Reson. Chem. 44 (2006) 553–565].

Novel nonlinear opticalphenomenain nematic liquid crystals

In normal materials, the nonlinear optical effects arise from nonlinearities in the polarisabilities of the constituent atoms or molecules. On the other hand the nonlinear optical effects in liquid crystals arise from totally different processes. Also they occur at relatively low laser intensities. In a laser field a liquid crystal exhibits many novel and interesting nonlinear optical effects. In addition we also find laser field induced effects that are peculiar to liquid crystals, like structural transformations, orientational transitions, modulated structures and phase transitions, to name a few. Here we dwell upon a few of these interesting and important nonlinear optical phenomena that exist in nematic liquid crystals.

Molecular Dynamics of Thermotropic Liquid Crystals: Anomalous relaxation dynamics of calamitic and discotic liquid crystals

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.

Study of liquid crystalline order by NMR

The liquid crystalline phase represents a unique state of matter where partial order exists on molecular and supra-molecular levels and is responsible for several interesting properties observed in this phase. Hence a detailed study of ordering in liquid crystals is of significant scientific and technological interest. NMR provides several parameters that can be used to obtain information about the liquid crystalline phase. Of these, the measurement of dipolar couplings between nuclei has proved to be a convenient way of obtaining liquid crystalline ordering since the coupling is dependent on the average orientation of the dipolar vector in the magnetic field which also aligns the liquid crystal.However, measurement of the dipolar coupling between a pair of selected nuclei is beset with problems that require special solutions. In this article the use of cross polarization for measuring dipolar couplings in liquid crystals is illustrated. Transient oscillations observed during cross polarization provide the dipolar couplings between essentially isolated nearest neighbor spins which can be extracted for several sites simultaneously by employing two-dimensional NMR techniques. The use of the method for obtaining heteronuclear dipolar couplings and hence the order parameters of liquid crystals is presented. Several modifications to the basic experiment are considered and their utility illustrated. A method for obtaining proton–proton dipolar couplings, by utilizing cross polarization from the dipolar reservoir, is presented. Some applications are also highlighted.

Computer simulation of liquid crystals

In this article we review the current status in the modelling of both thermotropic and lyotropic Liquid crystal. We discuss various coarse-graining schemes as well as simulation techniques such as Monte Carlo (MC) and Molecular dynamics (MD) simulations.In the area of MC simulations we discuss in detail the algorithm for simulating hard objects such as spherocylinders of various aspect ratios where excluded volume interaction enters in the simulation through overlap test. We use this technique to study the phase diagram, of a special class of thermotropic liquid crystals namely banana liquid crystals. Next we discuss a coarse-grain model of surfactant molecules and study the self-assembly of the surfactant oligomers using MD simulations. Finally we discuss an atomistically informed coarse-grained description of the lipid molecules used to study the gel to liquid crystalline phase transition in the lipid bilayer system.

Nucleation dynamics and pool boiling characteristics of high pressure refrigerant using thermochromic liquid crystals

This paper reports an experimental investigation of oscillating temperature field beneath a single isolated nucleation site using a non-invasive TLC (thermochromic liquid crystal) based thermography technique. Empirical correlations are presented to demonstrate the influence of system pressure and wall heat flux on different ebullition characteristics in the nucleate pool boiling regime of refrigerant R-134a. TLC transient response and two-phase flow structure are captured using synchronized, high resolution imaging. It is observed that the area of influence of nucleation site exhibits a two-part distinct transient behavior during the bubble growth period and broadens to a maximum of 1.57 times the bubble diameter at the instant of bubble departure. This is accompanied by a sharp fall of 2.5 degrees C in the local excess temperature at the nucleation site, which results in momentary augmentation (similar to 40%) in the local heat transfer coefficient at the nucleation origin. The enhanced heat transfer rate observed during the bubble peel-off event is primarily due to transient micro-convection in the wake of the retreating bubble. Further, the results indicate that a slight increase in system pressure from 813.6 to 882.5 kPa has no considerable effect on either the wall superheat or the overall heat transfer coefficient and ebullition frequency. In addition, correlations have been obtained for bubble Reynolds number, Jackob number and the dimensionless bubble generation frequency in terms of modified boiling number.

Molecular structure of the discotic liquid crystalline phase of hexa-peri-hexabenzocoronene/oligothiophene hybrid and their charge transport properties

Using atomistic molecular dynamics simulation, we study the discotic columnar liquid crystalline (LC) phases formed by a new organic compound having hexa-peri-Hexabenzocoronene (HBC) core with six pendant oligothiophene units recently synthesized by Nan Hu et al. Adv. Mater. 26, 2066 (2014)]. This HBC core based LC phase was shown to have electric field responsive behavior and has important applications in organic electronics. Our simulation results confirm the hexagonal arrangement of columnar LC phase with a lattice spacing consistent with that obtained from small angle X-ray diffraction data. We have also calculated various positional and orientational correlation functions to characterize the ordering of the molecules in the columnar arrangement. The molecules in a column are arranged with an average twist of 25 degrees having an average inter-molecular separation of similar to 5 angstrom. Interestingly, we find an overall tilt angle of 43 degrees between the columnar axis and HBC core. We also simulate the charge transport through this columnar phase and report the numerical value of charge carrier mobility for this liquid crystal phase. The charge carrier mobility is strongly influenced by the twist angle and average spacing of the molecules in the column. (C) 2015 AIP Publishing LLC.

Effect of polymer concentration on stabilized large-tilt-angle flexoelectro-optic switching

In this letter, the uniform lying helix (ULH) liquid crystal texture, required for the flexoelectro-optic effect, is polymer stabilized by the addition of a small percentage of reactive mesogen to a high-tilt-angle (φ>60°) bimesogenic chiral nematic host. The electro-optic response is measured for a range of reactive mesogen concentration mixtures, and compared to the large-tilt-angle switch of the pure chiral nematic mixture. The optimum concentration of reactive mesogen, which is found to provide ample stabilization of the texture with minimal impact on the electro-optic response, is found to be approximately 3%. Our results indicate that polymer stabilization of the ULH texture using a very low concentration of reactive mesogen is a reliable way of ruggedizing flexoelectro-optic devices without interfering significantly with the electro-optics of the effect, negating the need for complicated surface alignment patterns or surface-only polymerization. The polymer stabilization is shown to reduce the temperature dependence of the flexoelectro-optic response due to "pinning" of the chiral nematic helical pitch. This is a restriction of the characteristic thermochromic behavior of the chiral nematic. Furthermore, selection of the temperature at which the sample is ultraviolet cured allows the tilt angle to be optimized for the entire chiral nematic temperature range. The response time, however, remains more sensitive to operating temperature than curing temperature. This allows the sample to be cured at low temperature and operated at high temperature, providing simultaneous optimization of these two previously antagonistic performance aspects. © 2006 American Institute of Physics.

Experimental Study on Bénard-Marangoni Convection in Double Immiscible Liquid Layer

An experimental investigation of Bénard-Marangoni convection has been performed in double immiscible liquid layers of rectangular configuration on the ground. The two kinds of liquid are 10cst silicon oil and FC-70 respectively. The size of rectangular chamber is 100mm×40mm in horizontal cross-section. The evolution processes of convection are observed in the differential thickness ratio of two liquid layers. The critical temperature difference was measured via the detections of fluid convection by a particle image velocimetry (PIV) in the vertical cross-section of the liquid layer. The critical temperature difference or the critical Marangoni number was given. And the influence of the thickness ratio of two liquid layers on the convection instability was discussed. The evolution processes of patterns and temperature distributions on the interface are displayed by using thermal liquid crystal. The velocity distributions on the interface were also obtained. In comparison with the thermocapillary effect, the effect of buoyancy convection will relatively increase when the depth of the liquid layer increases. Because of the coupling of buoyancy and thermocapillary effect, the convection instability is much more complex than that in the microgravity environment. And the critical convection depends on the change of the thickness of liquid layers and also the change of thickness ratio of two liquid layers.