Computer Simulation of Biphenyl-Phenyl Ester Liquid Crystals

Abstract

Molecular orbital (MO) calculation and molecular dynamics (MD) simulation were carried out for a set of smectic liquid crystalline molecules, 8O-O8 (4-octyloxyphenyl-4′-octyloxybi-phenyl-4-carboxylate) and 8O-8 (4-octylphenyl-4′-octyloxybiphenyl-4-carboxylate), to understand the molecular origin of different crystalline structure formation and to predict their conformational property in liquid crystalline phases. The results of MO and MD analyses indicate that the structure of 8O-O8 and 8O-8 in crystalline phase is essentially determined by intramolecular interactions and the experimentally observed structure is chosen as a consequence of intermolecular packing constraints. This paper also reports the first application of two-molecular ab-initio calculation to liquid crystalline systems.     

The Smectic A and the Smectic C Phase: A Coherent Molecular Picture

A molecular field theory of the smectic A and smectic C phase is presented which is based on an interaction derived in terms of the molecular polarizability, its anisotropy and the components of the static molecular quadrupole tensor. It is shown that this attractive interaction strongly depends on the anisotropy of the excluded molecular volume. The results obtained explain the stability of the A phase, the appearance of the tilt in the C phase and the A-C phase transition, without resource to adjustable parameters which indeed have no molecular significance.     

Birefringence and Order Parameter of Some Alkyl and Alkoxycyanobiphenyl Liquid Crystals

The refractive indices and densities of six liquid crystals—two alkylcyanobiphenyls, three alkoxycyanobiphenyls and one mixture of two alkylcyanobiphenyls have been reported as a function of temperature. The effective polarizabilities α_eand α_o in the nematic phase calculated using the methods due to Neugebauer, Vuks and Saupe and Maier, are found to be appreciably different, though the order parameter S evaluated with those values of (α_e - α_o) are in good agreement. The preference of one method over the other two is discussed.     

Diamagnetic Anisotropy Measurements of Nematic Liquid Crystals

Electro-optic effect of liquid crystals in the presence of a magnetic field was investigated. Two independent techniques: magnetic field dependent threshold voltage and magnetic field-assisted relaxation time, were used to evaluate the diamagnetic anisotropy for three nematic liquid crystals: BDH-E7, RO-TN-103 and ZLI-1132. Correlation between the diamagnetic anisotropy and the molecular structures was obtained. This information is particularly important for synthesizing liquid crystal components with desired diamagnetic anisotropy.     

On the Origin of Trapping Centres in Organic Molecular Crystals

Traps for current carriers in molecular crystals may be due either to imperfections of the crystal structure (structural traps) or to chemical impurities introduced into the lattice (chemical traps). In the present paper simple hypotheses are presented explaining the formation of traps of the two groups. Perturbations of the crystal structure are not localized in one unit cell, but may extend over several farther cell. The local values of the polarization energy of the crystal lattice will change near to the centre of the defect, thus the “perturbed” molecules can act as traps for currentcarriers.Energetic distributions of traps as calculated under such conditions are foundto be in a good agreement with those determined experimentally. Trapping states may be also formed by impurity molecules having either greater electron affinity or smaller ionization energy than the host ones. The depth of the chemical traps estimated from the relationships given in the paper has been compared with the experimental data.     

Synthesis and Some Properties of Low Melting Ferroelectric Liquid Crystals of Benzylidene Anilines

A series of chiral benzylidene-aniline compounds, 4-alkoxybenzylidene 4′-(2-methylbutyloxycarbonyl)anilines, have been synthesized and their mesomorphic properties are examined. They showed a monotropic chiral smectic C phase in conjunction with enantiotropic smectic A phase, and their chiral smectic C—smectic A phase transition temperatures are around room temperatures. Their spontaneous polarization values are moderately higher than those of DOBAMBC “4-decyloxybenzylidene 4′-amino-(2-methylbutyl)cinnamate”.     

Synthesis and Crystal Structure of Mono-Substituted Ferrocene-Containing Liquid Crystals

Abstract

Ten mono-substituted ferrocene-containing liquid crystals, which containing Schiff base or ester group, were prepared and their mesogenic behaviors were investigated. Two molecular structures were analyzed by X-ray. 4-ferrocenylphenyl 3′-chloro-4′-(2-methylbutyloxy)-benzoate, triclinic crystal system, P1 space group, a=12.035(2)Å, b=14.402(3)Å, c=15.137(3)Å, α =103.07(3)Å, ß = 102.01(3)Å, γ = 96.70(3)Å, Z=4, 8141 independent reflections, R=0.0528, Rw=0.1724. 4-ferrocenylphenyl 3′-chloro-4′-decanyloxybenzoate, triclinic crystal system, P1 space group, a= 11.663(2)Å, b= 11.729(2)Å, c=22.005(4)Å, α=76.10(3)Å, ß =87.56(3)Å, γ = 77.89(3)Å, Z=4, 7935 independent reflections, R=0.0784, Rw=0.2265.     

Synthesis and Mesomorphic Behavior of Calamitic Liquid Crystals with a Biphenyl Moiety

A new mesogenic homologous series having a biphenyl moiety has been synthesized by condensing 4-hydroxy-4′-nitrobiphenyl- and methoxy-substituted 4-n-alkoxy cinnamoyl chlorides, and their liquid crystalline properties have been studied. All the members of the series are enantiotropic liquid crystals. The methyl to n-pentyl derivatives exhibit both Smectic A (SmA) and Nematic (N) phases; the higher members, starting with the n-hexyl derivative show only a SmA phase. The plot of transition temperatures versus number of carbon atoms in the alkoxy chain exhibits zig-zag pattern for Sm-N and N-Isotropic (Iso) transition temperature curves. The average thermal stability is compared with other related homologous series. The introduction of polar nitro group increases significant intermolecular force of attraction which stabilizes the molecular orientation. This results into the increase in the thermal stability of the system.     

Liquid Crystal Channel Waveguides: A Monte Carlo Investigation of the Ordering

We present detailed Monte Carlo (MC) simulations of a nematic cell with homeotropic boundary conditions at the four confining surfaces. The simulations are based on the Lebwohl-Lasher lattice spin model with boundary conditions chosen to mimic the cell anchoring. We have investigated the model using a standard Metropolis Monte Carlo method to study the optical transmission and the ordering through the cell.     

Smectic phases of liquid crystals based on dinuclear palladium(II) complexes with carboxylato bridge

In this paper we present the preparation and the investigation of the liquid crystal properties of a series of dinuclear carboxylato bridge Pd(II) complexes bearing six alkoxy peripheral chains in the molecule. Their structures were assigned based on elemental analysis, IR and ¹H NMR spectroscopy whereas the thermal behaviour was investigated by polarizing optical microscopy and differential scanning calorimetry. The monotropic smectic A phase displayed by these materials was identified by miscibility studies with a previously reported mesogen. It was found that the transition temperatures and the SmA mesophase stability depend on the alkyl chain length of the carboxylato bridge. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nonlocal Continuum Theory of Liquid Crystals

A nonlocal continuum theory of liquid crystals is constructed to explain and predict the physical behavior of liquid crystals under long range intermolecular forces Balance laws consist of conservation of mass and mocroinertia, balance of momenta and energy. Constitutive equations are given for the equibilibirium and non-equilibirium parts of the stress, couple strees, free energy, entropy an nonlocal body force and couple. Thermodynamic restrinctions and material frame-indifference are studied. The theory is valid for liquid crystals having arbitrary shapes (inertia), Passage is made to the thread-like molecuels and to local theory. Applications are considered to two-dimensional problmes, steady, plane shear flows and disperison of twist waves.     

Surface Order Parameter and Polar Anchoring Energy in Nematic Liquid Crystals

The trends of temperature dependence of the surface order parameter and of the anchoring strength coefficient are theoretically evaluated in the Landau-de Gennes phenomenological theory for nematic liquid crystals. The cases of planar, homeotropic and tilted alignment at a planar limiting surface are considered. It is shown that the cases with surface order parameter greater than the bulk one or smaller than this can occur in function of the phenomenological coefficients in the surface free energy expression. The anchoring strength coefficient, W, diminishes when temperature approaches the nematic-isotropic point, after passing through a maximum in most of cases. The possibility of a non-zero anchoring strength at temperatures above the transition temperature is revealed. The obtained trends of W(T) describe well a large variety of experimental results from literature.     

Vibrational Spectra of Liquid Crystals. XII

Abstract

Recent papers by Gray et al.¹ have discussed the synthesis, structure, and properties of the mesomorphic 4-cyano, 4′-alkyl (or alkoxy) biphenyls. The reports on these materials have made mention of the existence of solid state dimorphism for certain homologs. This paper discusses this dimorphism as it manifests itself in the Raman spectrum of the octyloxy homolog (hereinafter referred to as 80CB) in the CN stretching region.

The approach used involves direct measurement of the Raman spectrum as a function of temperature, as well as computation of a correlation function obtained from the Raman band envelope by means of Fourier transformation. The application of this correlation function technique to this system has been discussed by us recently in detail.^2,3

Gray and Mosley,⁴ in a recent study of the Raman spectrum of 4-cyano, 4′-pentylbiphenyl note that the CN stretch of this compound is a doublet in the solid phase (2224 and 2233 cm^?1), but only the 2224 cm^?1 band appears in the nematic phase. They further report that only a single band appears in the CN stretching spectrum of solid 4'-heptyl-, -hexyl-, and -butyl-derivative. They speculate that the doublet might appear in the spectrum of the metastable solid phase of the heptyl homolog.

In this work, we show that for 80CB this is not the case. Rather, a doublet is observed for the stable solid but not for the metastable. The origin of this doublet is discussed, and all of the CN stretches for stable solid, metastable solid, and smectic liquid crystal are analyzed from the viewpoint of the vibrational relaxation correlation function.     

Smectic A-Nematic and Nematic-Isotropic Liquid Transitions in 8CB Liquid Crystal: Comparative Analysis

A differential heat flux calorimeter has been used to study the Smectic A-Nematic and Nematic-Isotropic Liquid transitions in 8CB liquid crystal. The Faktor and Hanks model under our working conditions enables us to distinguish first-order from second-order transitions by analysis of differential signal. The critical exponent values obtained justify the proportionality between Cp evolution and the normalized differential signal (differential signal divided by the scanning rate).     

Application of Infrared ATR Spectroscopy to Liquid Crystals. III

Infrared absorption measurements of nematic N-(p-ethoxybenzylidene)-p'-cyanoaniline (EBCA) under a DC electric field were performed by means of our previously reported ATR method. DC voltages up to 15V were applied to the nematic liquid crystal 15 μm thick between a silicon ATR prism (probing electrode) and an In₂O₃-coated glass electrode (opposite electrode). By using this method the orientational behavior of molecules in boundary layers about 1 μm thick at the Si electrode was investigated.

The threshold voltage for the dielectric orientation varied from 2 to 6 V depending upon the boundary conditions at the opposite electrode, and the maximum degree of order of homeotropic orientation was found to be 0.6–0.7. A storage effect, in which a homeotropic texture induced by the electric field remains unaltered even if the field is removed or reversed, was observed.     

Electrical and Optical Properties of Ferroelectric Liquid Crystals and Influence of Applied Pressure

Much larger dielectric constants and spontaneous polarizations are evaluated in the smectic-C phase of p-alkoxybenzylidene-p'-amino-2-chloropropyl-cinnamate (HOBACPC, OOBACPC and DOBACPC) which have dipole moments at the chiral part compared with those of p-alkoxybenzylidene-p'-amino-2-methylbutyl-cinnamate. In the mixture of D-DOBAMBC and L-DOBACPC with inverse chirality, the pitch of the helical structure is longer compared with those of original compounds. On the other hand, the dielectric constant and the spontaneous polarization of the compounds are nearly linearly dependent on the concentration of L-DOBACPC.

The phase transition temperature from smectic-A to chiral smectic-C phases in DOBAMBC decreases remarkably with the mixing of organic molecules (PAA, eicosane, etc.) but increases with applied pressure.

The threshold field of electro-optical effects (transmission increase, colour switching, memory effects) in DOBACPC and HOBACPC etc. is lower than that in DOBAMBC etc. in accordance with the increase of the spontaneous polarization in the former.     

Photo Controlled Surfaces in Rheology of Liquid Crystals

The modified method for shear viscosity measurements of nematic liquid crystals (NLC) oriented by surfaces is described. The main modification is concerned with usage of photoalignment technique for preparation of mono-domain samples with an orientation controlled by a polarization state of the secondary light irradiation. It provides the azimuthal rotation of a sample at any desirable angle. Thus different geometries of shear flows can be realized after filling the measuring cell with a liquid crystal. The method is experimentally approved at investigation of Poiseuille decay flows of 4-pentyl-4-cyanobiphenyl (5CB) through the channels with a rectangular cross section. The proposed construction of the cell with different surface treatment provides measurements of the three principal viscosities coefficients (Miesowicz’ viscosities) with additional usage of electric field. A small amount (less than 0.2 ml) of a liquid crystal needed for measurements and simple measuring procedure makes the method to be useful for rheological studies of newly synthesised liquid crystal materials.     

Anisotropic Atomic Displacement Parameters and Molecular Motions in Mesogenic Crystals

Abstract

In this paper we describe the results of vibrational analysis of molecules in the crystalline phase of three mesogenic compounds of the series n-alkyl cyclohexyl cyanophenyl pyrimidine from experimental atomic displacement parameters using the rigid body model of Cruickshank. The rigid body model has been applied so far for estimation of corrections in bond lengths arising from the librational modes of motion. We have undertaken this vibrational analysis to find out whether we can get any idea about the transition from crystalline to liquid crystalline phase. Two tensors T (translation) and L (libration) are used to describe the motion. These tensors have been diagonalized to obtain the principal axes and amplitudes of translational and librational motions.