Modelling a nematic liquid crystal

The bulk phase liquid crystalline behaviour of a cyclic siloxane with a pentamethylcyclosiloxane core and biphenyl-4-allyloxybenzoate mesogens (BCS) was studied using molecular dynamics (MD) and wide angle X-ray analysis. This material exhibits partial crystallinity at room temperature and liquid crystalline behaviour above 120° C. For the MD simulations an ensemble of 27 molecules with 135 mesogenic units was simulated and a molecular mechanics force field was used to model the structural anisotropy of the siloxane molecules. Simulations were carried out both at room temperature and at an elevated temperature (425 K). Room temperature simulations showed that, contrary to our initial assumptions, the low energy molecular conformations were not cylindrical but splayed in shape. During the simulation a smectic-like, tilted layer structure was found to evolve for the cluster when full atom potentials were used, while no such development was observed when electrostatic interactions were neglected. The presence of a tilted layered structure was also suggested by the X-ray data. These results indicate that long range electrostatic interactions are significant for the molecular system under study. In order to calculate the orientational order parameter, the orientation of the molecular axis had to be determined. This was achieved by describing the mesogen shapes to be ellipsoidal and defining the principal axis of the ellipsoids to be the molecular directors. By sampling over 200 ps of simulation at 425 K, the time averaged order parameter (S) was calculated. The calculated S of 0.36 was comparable to the value of 0.4-0.45 found from the experimental data. Apart from providing insight into the relative importance of the various competing forces in the formation of the liquid crystalline phase, these simulations are also expected to be useful in predicting the mesophase behaviour of liquid crystalline systems.     

Kinetics of proton transfer between semiquinone and nitroxyl radicals

The kinetic parameters of the fast reversible reaction of proton transfer between paramagnetic proton donors: 3,6-di-tert-butyl-2-hydroxyphenoxyl, 4,6-di-tert-butyl-3-chloro-2-hydroxyphenoxyl, 4-triphenylmethyl-6-tert-butyl-3-chloro-2-hydroxyphenoxyl, and paramagnetic proton acceptors, nitroxy radicals containing nitrogen heterocycles were estimated by EPR. It was found that proton transfer between paramagnetic acid and base takes place with a higher rate than the analogous reaction between substituted 2-hydroxyphenoxyl and a diamagnetic base.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 65–70, January, 1991.     

Mass transport in a chiral nematic/nematic liquid crystal system

The optical microscopic mass transport technique has been used to study diffusion phenomenon in a chiral nematic/nematic solute/solvent mixture. Analysis of the concentration-distance, concentration-time and distance-time of the diffusion profile gave the diffusion coefficient of the system as a function of time, distance and concentration, respectively. The mutual diffusion coefficient of the system was independent of the distance and time, showing an average value of 2.65 × 10^-7 cm² s^-1. In non-steady state diffusion, the diffusion coefficient was dependent on both distance and time. The diffusion coefficient exhibited an inverse relation with the local concentration of the chiral solute. The self-diffusion coefficient of the nematic solvent gave a value of 3.4 × 10^-7 cm² s^-1 via extrapolation to zero concentration of the solute.     

Ising wall instability in a nematic liquid crystal

A new instability for a splay-bend Ising wall was found in a 5CB nematic liquid crystal layer. This instability, which occurs in the presence of an external horizontal magnetic field, is driven by the elastic anisotropy of the liquid crystal material. Depending on the homogeneity of the magnetic field, the unstable straight interface evolves towards a new steady state or undergoes a spinodal decomposition into facets. Energy arguments are given in order to explain these physical phenomena.     

NMR polarization echoes in a nematic liquid crystal

We have modified the polarization echo (PE) sequence through the incorporation of Lee-Goldburg cross polarization steps to quench the 1H-1H dipolar dynamics. In this way, the 13C becomes an ideal local probe to inject and detect polarization in the proton system. This improvement made possible the observation of the local polarization P(00)(t) and polarization echoes in the interphenyl proton of the liquid crystal N-(4-methoxybenzylidene)-4-butylaniline. The decay of P(00)(t) was well fitted to an exponential law with a characteristic time tau(C) approximately 310 micros. The hierarchy of the intramolecular dipolar couplings determines a dynamical bottleneck that justifies the use of the Fermi Golden Rule to obtain a spectral density consistent with the structural parameters. The time evolution of P(00)(t) was reversed by the PE sequence generating echoes at the time expected by the scaling of the dipolar Hamiltonian. This indicates that the reversible 1H-1H dipolar interaction is the main contribution to the local polarization decrease and that the exponential decay for P(00)(t) does not imply irreversibility. The attenuation of the echoes follows a Gaussian law with a characteristic time tau(phi) approximately 527 micros. The shape and magnitude of the characteristic time of the PE decay suggest that it is dominated by the unperturbed homonuclear dipolar Hamiltonian. This means that tau(phi) is an intrinsic property of the dipolar coupled network and not of other degrees of freedom. In this case, one cannot unambiguously identify the mechanism that produces the decoherence of the dipolar order. This is because even weak interactions are able to break the fragile multiple coherences originated on the dipolar evolution, hindering its reversal. Other schemes to investigate these underlying mechanisms are proposed.     

Ising wall instability in a nematic liquid crystal

A new instability for a splay-bend Ising wall was found in a 5CB nematic liquid crystal layer. This instability, which occurs in the presence of an external horizontal magnetic field, is driven by the elastic anisotropy of the liquid crystal material. Depending on the homogeneity of the magnetic field, the unstable straight interface evolves towards a new steady state or undergoes a spinodal decomposition into facets. Energy arguments are given in order to explain these physical phenomena.     

Propagative patterns in the convection of a nematic liquid crystal

We show here that the convective instability of a nematic liquid crystal subjected to an A.C. electric field (the conduction regime), is never stationary, contrary to the widely accepted picture. Indeed, we have found that the roll structure translates uniformly along the wavevector direction. In the low frequency part of the conduction regime, the structure is rather homogeneous in space and travels at a very low velocity, while inside the high frequency part, the rolls are localized inside stable domains and the propagation velocity is higher by three orders of magnitude. Closer to the cut-off frequency, we have also found a novel time dependent state, where the amplitude of the rolls oscillates periodically in time.     

Dynamics of a nanowire in twisted nematic liquid crystal

The dynamics of a nanowire immersed in a nematic liquid crystal sandwiched between two parallel plates are studied by applying an equivalent capacitance approach used in electrostatics. A lower cut-off eigenfrequency for the oscillation of the nanowire is found and the lighter the mass, the smaller the critical cell separation at which the cut-off frequency occurs is needed. A simulation of the dynamical process of the metal wires shows that the relaxation time is proportional to η/m in the small mass region.     

Enhancement of flexoelectric ratio of nematic liquid crystal by doping calamitic ferroelectric liquid crystal

We measured the flexoelectric ratio e* of a nematic liquid crystal (NLC) doped with a calamitic ferroelectric liquid crystal (FLC). We doped two kinds of commercial FLC into the pure NLC at a weight concentration of 5 wt%. The absolute value of the flexoelectric ratio was increased up to 49% compared to the pure NLC. The greater transverse dipole moment and the elastic constant of FLC are thought to be related to the increase of the flexoelectric ratio.     

Shear-induced rotations in a weakly anchored nematic liquid crystal

We analyse the instability dynamics of a nematic liquid crystal under steady plane Couette flow. Weak anchoring for molecules of the nematic at the boundaries with an easy axis perpendicular to the flow plane is assumed. Orientation of the director along the easy axis is our basic state. Previously (Tarasov et al., 2001, Liq. Cryst. 28, 833), it was found that the critical shear rate of the primary instability of the basic state strongly decreases with anchoring strength. In the present study our interest was to examine the effect of the anchoring strength on the nematic dynamics in the regime with a slightly supercritical shear rate. It was found that for weaker anchoring the director rotates more strongly and the relaxation time of the amplitude of the basic state perturbations significantly increases. Results obtained can be used for experimental measurements of the anchoring strengths.     

Flexoelectro-optic effect in a hybrid nematic liquid crystal cell

W e analyse the influence of charged impurities and flexoelectric polarization on the optical transmission of a hybrid aligned nematic liquid crystal cell. The theoretical results obtained within the framework of the Poisson-Boltzmann equation and Frank elastic theory are compared with the observed optical response [N. V. Madhusudana and G. Durand,J. Phys.Lett. 46, L-195 (1985)]. We show that impurities can be very important for the behaviour of the system in the low field regime where the flexoelectric effect is relevant, and we determine the flexoelectric coefficient, the anchoring strength, and the concentration of impurities in the sample previously studied by Madhusudana and Durand.     

Orientational fluctuations in a nematic liquid crystal as seen by neutron scattering

Abstract

Real time neutron scattering is used in the study of the slow orientational fluctuations of the director in a nematic sample. A statistical analysis of the observed time series gives the Hurst exponent H and β exponent of the frequency power spectrum that satisfy the scaling relationship β = 2H + 1. In the nematic phase, but not in the solid and in the isotropic liquid phases, the exponent values are those expected for a self-organized critical state. When a magnetic field, of the order of the Freedericksz field is applied, the nematic sample is observed to display persistent oscillations of the director. We confront this observation with theoretical predictions.     

Instabilities of nematic liquid crystal films

We discuss instabilities exhibited by free surface nematic liquid crystal (NLC) films of nanoscale thickness deposited on solid substrates, with a focus on surface instabilities that lead to dewetting. Such instabilities have been discussed extensively; however, there is still no consensus regarding the interpretation of experimental results, appropriate modeling approaches, or instability mechanisms. Instabilities of thin NLC free surface films are related to a wider class of problems involving dewetting of non-Newtonian fluids. For nanoscale films, the substrate–film interaction, often modeled by a suitable disjoining pressure, becomes relevant. For NLCs, one can extend the formulation to include the elastic energy of the NLC film, leading to an ‘effective’ disjoining pressure, playing an important role in instability development. Focusing on thin film modeling within the framework of the long-wave asymptotic model, we discuss various instability mechanisms and outline problems where new research is needed.     

Crystallisation of nematic liquid crystal mixtures

In this paper, we propose a method to accelerate the crystallisation of nematic liquid crystal mixtures based on crystallisation theory. This method is to hold a nematic liquid crystal sample at a temperature suitable for crystal growth after aging it at a temperature suitable for nucleation. After we specified these temperatures of a nematic liquid crystal mixture using differential scanning calorimetry, we demonstrate that the two-temperature aging method is effective for the crystallisation of other nematic liquid crystal mixtures in which the crystal-liquid crystal transition temperature has so far been undetectable.     

Glass formation in the Gay-Berne nematic liquid crystal

We present the results of molecular dynamics simulations of the Gay-Berne model of liquid crystals, supercooled from the nematic phase at constant pressure. We find a glass transition to a metastable phase with nematic order and frozen translational and orientational degrees of freedom. For fast quench rates the local structure is nematic-like, while for slower quench rates smectic order is present as well.     

Kinetics of the reduction of organic cations by cation radicals

It has been found that the reduction of substituted diazonium, iodonium, and tropylium salts by cation radicals of tetra-tert-butyl-bis-pyrylium, tetramethyl-p-phenylene diamine (I), tetraphenylbenzidine, and N-methylphenothiazine obey the kinetic equation of the second order and that it follows an electron transfer mechanism. The logarithms of the rate constants of these reactions decrease with increasing standard free energy of the electron transfer reaction. The rate of the reaction of C₆H₅N₂₊ BF₄ ^– with I and the selectivity of the reactions of the substituted diazonium salts with I increases with the electron donor capacity of the solvent. The addition of crown-ethers accelerates the reaction. The reaction rate increases also with increasing ionic strength of the solution, whereby the Cl^– anions have a specifically accelerating effect. The observed rules governing the influence of the medium contradict those found earlier for the interaction of organic cations with neutral radicals and anion radicals. This is attributed to the fact that the electron transfer takes place in ternary complexes cation-solvent (crown ether, Cl^– ion)-cation radical.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 1, pp. 45–51, January–February, 1985.The authors wish to express their gratitude to V. V. Lobonov for tje performance of the quantum chemical calculations.     

Dynamics of surface anchoring breaking in a nematic liquid crystal

Abstract

We present a simple dynamical model which describes the time dependence of the threshold electric field for breaking the surface anchoring of nematics. This model includes a surface friction, resulting from volume hydrodynamic dissipation. Experimental data with AC and DC pulsed fields are explained by this model. For DC, the threshold difference versus the field polarity is well-described by the flexo-electric effects in a uniform field for short times and in a non-uniform field for long times.     

Dynamics of surface anchoring breaking in a nematic liquid crystal

We present a simple dynamical model which describes the time dependence of the threshold electric field for breaking the surface anchoring of nematics. This model includes a surface friction, resulting from volume hydrodynamic dissipation. Experimental data with AC and DC pulsed fields are explained by this model. For DC, the threshold difference versus the field polarity is well-described by the flexo-electric effects in a uniform field for short times and in a non-uniform field for long times.