Thresholdless switching induced by polar anchoring in antiferroelectric liquid crystals

We present a novel thresholdless switching mode in an antiferroelectric liquid crystal cell which is stabilized by the presence of polar anchoring at the cell surfaces and the antiferroelectric nature of the material. We also suggest other possible configurations which are induced by strong polar anchoring and possess quite different director structures and optical characteristics.     

Thresholdless switching induced by polar anchoring in antiferroelectric liquid crystals

We present a novel thresholdless switching mode in an antiferroelectric liquid crystal cell which is stabilized by the presence of polar anchoring at the cell surfaces and the antiferroelectric nature of the material. We also suggest other possible configurations which are induced by strong polar anchoring and possess quite different director structures and optical characteristics.     

Banana-shaped liquid crystals with two oligosiloxane end-groups: field-induced switching of supramolecular chirality

The first bent core mesogen carrying branched oligosiloxane units at both ends was synthesized and investigated with polarized light microscopy, DSC, X-ray diffraction of well aligned samples, and electrooptical methods. Two different antiferroelectric switching liquid crystalline phases were found. Both can be regarded as modulated smectic phases in which the molecules have extremely large tilt angles. In both mesophases, the field-induced switching takes place by rotation around the molecular long axes. This field-induced reorientation switches the layer chirality. The transition between the two mesophases is associated with a change of the tilt direction from synclinic to anticlinic. The synclinic high-temperature phase is an obliquelike ribbon phase whereas the anticlinic low-temperature phase represents a sinusoidal undulated layer structure (SmCAPA). It is proposed that the phase transition from the ribbon phase to the undulated layer structure is mainly driven by the change of the interlayer correlation.     

Ferrielectric and antiferroelectric chiral twin liquid crystals showing a stable chiral nematic phase

A homologous series of chiral twin liquid crystals possessing identical chiral moieties at both peripheral ends, i.e. optically active α,ω -bis{4-[(4′-(1-methylheptyloxycarbonyl)-4-biphenylyl)oxycarbony]phenoxy}alkanes, has been prepared and their liquid crystalline properties investigated. The homologues preferred to show the ferrielectric and/or antiferroelectric phase rather than the ferroelectric phase. With ascending central spacer length, the temperature range of the ferrielectric phase became narrow and eventually disappeared for the dodecyl homologue, suggesting that the coupling in motion and/or direction between two mesogenic parts of each twin molecule has an important effect on the stabilization of the ferrielectric phase. The octyl and dodecyl homologues showed a wide temperature range chiral nematic phase (ca. 10°C or more), so that these compounds were found to be the first examples showing antiferroelectric and/or ferrielectric phases with a broad temperature range of the chiral nematic phase. X-ray diffraction studies showed that the homologues tend to form a mono-layered structure. The formation of a relatively well defined layered structure was also indicated, which is considered to be important for generating anticlinic ordering in the antiferroelectric and ferrielectric phases. An isotropic-isotropic transition characterized by the emergence of a broad diffuse DSC peak was observed for the even-membered homologues.     

Electric field effects in nematic layers with weak boundary anchoring

The stationary states induced by an electric field in nematic layers with weak boundary anchoring are described by means of the Taylor expansion method based on catastrophe theory. The planar, twisted and supertwisted structures are considered. The analysis is extended to materials with negative dielectric anisotropy. Several types of behaviour are found. The possibility of switching between twisted and homeotropic states is suggested.     

Several types of bilayer smectic liquid crystals with ferroelectric and antiferroelectric properties in binary mixture of dimeric compounds

The mesomorphic behavior and phase structure were examined in the mixture of two kinds of dimeric compounds, alpha,omega-bis(4-alkoxyanilinebenzylidene-4'-carbonyloxy)pentane (mOAM5AMOm), by optical microscopy, X-ray diffraction, polarization switching, and second-harmonic generation measurements. One compound is 4OAM5AMO4 with a short terminal alkyl chain that forms a single-layer smectic phase (SmCAs) with a random mixing of spacer and tail groups. Another compound is 16OAM5AMO16 with a long terminal alkyl chain that forms a chiral, anticlinic, and antiferroelectric bilayer phase (SmCAb) with the bent molecules tilted to the bilayer. By mixing these two compounds, the SmCAs phase of 4OAM5AMO4 is easily destabilized, leading to the wide content region of the bilayer phases. In the bilayer regime, three other smectic phases are newly induced. Two of them are antiferroelectric and ferroelectric phases in which the molecules lie perpendicularly with respect to the layer. The other shows no polar response to an external electric field and behaves like a smectic A. The new appearance of these bilayer phases is discussed as a mixing effect of long and short tail groups.     

Communication: Experimental proof of symmetry breaking in tilted smectics composed of molecules with axial chirality

For the first time, domains with twisted structures have been established in planar samples of achiral compounds in tilted smectic C phase. This evidences separation of molecular conformers differing in the sense of axial chirality and confirms polar C(2) symmetry of these domains. A simple model considering polar surface anchoring energy and bulk energy of the twist can account for this finding. Conditions for coexistence of twisted and homogeneous domains are discussed.     

Layer frustration, polar order and chirality in liquid crystalline phases of silyl-terminated achiral bent-core molecules

A novel class of bent-core molecules with oligo(siloxane) or carbosilane units at both ends was synthesized and the self-organization of these molecules was investigated by polarizing microscopy, DSC, X-ray scattering, dielectric and electrooptical methods. Depending on the size of the silicon-containing segments, smectic and columnar liquid crystalline phases are formed. Most smectic phases are low birefringent and composed of macroscopic domains of opposite handedness (dark conglomerate phases). The switching process in these smectic phases is surface stabilized ferroelectric and, depending on the conditions, two distinct slow relaxation processes to nonpolar structures were observed. It is proposed that the smectic phases are built up by chiral and polar SmCsPF layer stacks which are separated by anticlinic interfaces. If the size of these layer stacks is sufficiently large a coupling to the substrate surfaces takes place and ferroelectric switching is observed. It is also suggested that the sponge-like layer distortion, occurring in the low birefringent mesophases, is due to an escape from the local polar order within these SmCsPF layer stacks. For compounds with larger silylated units a steric frustration arises, which leads to layer modulation (columnar ribbon phases) and this is associated with a transition from ferroelectric to antiferroelectric switching. All compounds show a switching of the molecules around the long axis which reverses the layer chirality.     

Effect of weak anchoring on the electric field induced deformations of nematic layers

The stationary deformations of nematic layers with a twisted structure are analysed by means of the Taylor expansion method based on catastrophe theory. The role of weak anchoring is investigated. Variations of the polar and azimuthal angles describing the surface director orientation are allowed. The stability of two equilibrium states, the twisted and the homeotropic, is studied. Several types of continuous and discontinuous transitions between them are revealed. The threshold voltages are calculated.     

A Driven Voltage-Controlled Reversible Electrooptic Effect in a Smectic A Phase II. PVA Anchoring

Abstract

The driven voltage-controlled reversible electrooptic effect in a smectic A phase with a preceding nematic phase twisted by SiO anchoring, previously discovered (cf. the previous paper) has been studied with polyvinyl alcohol (PVA) anchoring. The unique feature of this novel electrooptic effect in smectic A phases is that it reverses by relaxing when the electric field is removed. For the case of PVA anchoring the reversibility of the effect only occurs near the smectic A-nematic phase transition in the smectic A phase. The temperature region of the reversibility of this effect can be widened with a higher voltage. A comparison with the case of a reversible electrooptic effect in a smectic A with a preceding twisted nematic phase and SiO anchoring is made. The possible application of this electrooptic effect in liquid crystal displays with storage is discussed briefly.     

Quantum chemical study of self-organized water fractals

The energetically possible ways of water condensation at the molecular level were considered. The quantum chemical calculations of the relative stability of elementary modules of the fractal structure without external fields using AM 1, CNDO /2, and MNDO methods were done. It was shown that CNDO /2 gives the most adequate results for simple water clusters. Condensation energy per molecule was chosen as a criterion of the cluster stability. It was shown that the twisted modules are the stable structures with respect to the water dissociation. In comparing the energies of the icelike and twisted structures, we conclude that the latter may exist under certain conditions. © 1996 John Wiley & Sons, Inc.     

Antiferroelectric behavior in a liquid crystalline polymer

Electro-optic and polarization reversal measurements were performed on a side-chain polymer exhibiting a chiral smectic phase. Based on the observed electro-optic and current responses, we discuss the possibility of an antiferroelectric structure in the polymer. In order to establish a model for the observed behavior, a detailed comparison with the properties of the low molar mass antiferroelectric substance MHPOBC was made. The birefringence modulation in the chiral smectic polymer, originating from the field-induced antiferroelectric-to-ferroelectric transition, is analyzed for the case of a randomly oriented sample. The result shows that the coincidence of birefringence modulation and polarization current peaks is strong evidence for the existence of antiferroelectric order in the smectic layers. Such coincidence was observed both for MHPOBC and the chiral side-chain polyacrylate.     

A Driven Voltage-Controlled Reversible Electrooptic Effect in a Smectic A Phase II. PVA Anchoring

The driven voltage-controlled reversible electrooptic effect in a smectic A phase with a preceding nematic phase twisted by SiO anchoring, previously discovered (cf. the previous paper) has been studied with polyvinyl alcohol (PVA) anchoring. The unique feature of this novel electrooptic effect in smectic A phases is that it reverses by relaxing when the electric field is removed. For the case of PVA anchoring the reversibility of the effect only occurs near the smectic A-nematic phase transition in the smectic A phase. The temperature region of the reversibility of this effect can be widened with a higher voltage. A comparison with the case of a reversible electrooptic effect in a smectic A with a preceding twisted nematic phase and SiO anchoring is made. The possible application of this electrooptic effect in liquid crystal displays with storage is discussed briefly.     

Numerical analysis of the radial-axial structure transition with an applied field in a nematic droplet

In this paper the director configurations and the free energies of a nematic droplet with a surface normal anchoring condition are calculated numerically. For this surface anchoring, a transition occurs between the radial and axial structures with respect to an applied field. In the calculation of the director configurations, the position of a disclination has been fixed. Comparing the free energies for different disclinations, the stable position which gives the minimum free energy is found. In calculating the free energy of a droplet, it is assumed that the free energy density of the nematic phase does not exceed the isotropic free energy density, so that the large distortion in the vicinity of the disclination causes a nematic-isotropic transition and the free energy density of the disclination core becomes equal to the isotropic free energy density. The director configuration in a droplet is calculated as a function of an applied field for different isotropic free energy densities, elastic constant ratios and droplet shapes. The relation between the radial-axial structure transition and these factors are clarified.     

Scroll wave filaments terminate in the back of traveling fronts

Experiments with the 1,4-cyclohexanedione Belousov-Zhabotinsky reaction demonstrate that three-dimensional scroll waves can rotate around filaments that end in the wake of a traveling excitation pulse. The vortex structures nucleate during the collision of three nonrotating excitation pulses. The nucleation process and the wave-termination of filaments are direct consequences of the system's anomalous dispersion relation. Vortex filaments are found to expand with about twice the speed of their anchoring wave fronts. Filament expansion is accompanied by the build-up of phase differences in spiral rotation creating strongly twisted wave structures. Experiments employ optical tomography for the reconstruction of the three-dimensional wave patterns.     

The S1 ← S0 0–0 transition energies of polychlorinated dibenzofurans (PCDFs) revisited: CIS(D) and MP2 calculations with correction for correlation energies

This paper reexamines the structures and energies of dibenzofuran and twenty PCDFs in S₁–S₃ states. It was demonstrated that, although the CIS method gives a false relative ordering of excited states, the false ordering can be remedied by the CIS(D) method. Moreover the CIS geometries of typical PCDF molecules reasonably agree with their SAC-CI geometries. It was found that molecules chlorinated at the 1- and 9-positions are twisted in the S₂ state but are planar in other states, except for 1,4,6,9-TeCDF and fully chlorinated dibenzofuran (OCDF). The twisted structure of 1,4,6,9-TeCDF occurs in the S₃ state, but the structure of OCDF is twisted in every state. We partitioned the molecule into the parent structure and four chlorine groups and measured the twist energy with reference to the ground state. Then, the S_i ← S₀ 0–0 transition energies (i = 1, 2) calculated using the CIS(D) and MP2 methods could be expressed as a multiple linear equation with components and twist energy. It was further confirmed that if the multiple linear equation is corrected for residual correlation energies of the parent structure, it can predict the S₁ ← S₀ 0–0 transition energies with high precision.     

Orientational transition in the cholesteric layer induced by electrically controlled ionic modification of the surface anchoring

A reorientation of cholesteric liquid crystal with a large helix pitch induced by the electrically controlled ionic modification of the surface anchoring has been studied. In initial state, the cholesteric helix is untwisted completely owing to the normal surface anchoring specified by the cations adsorbed at the substrates. As a result, the homeotropic director configuration is observed within the cell. Under the action of DC electric field, one of the substrates becomes free from the layer of surface active cations, therefore, setting the planar surface anchoring. The latter, in turn, leads to the formation of the hybrid chiral structure. The threshold value and dynamic parameters have been estimated for this process as well as the range of control voltages, which do not allow the electrohydrodynamic instabilities. The twisted hybrid director configuration observed in the experiment has been analysed by means of the simulation of polarisation change of light propagating through the cholesteric layer with asymmetric (planar and homeotropic) surface anchoring on the cell substrates.     

Theoretical investigation of luminescence behavior as a function of alkyl chain size in 4-aminobenzonitrile alicyclic derivatives

There is still controversy about the structure of the intramolecular charge transfer (ICT) emitting species in pi-electron donor-acceptor systems that show dual fluorescence. Although the twisted ICT model is quite generally accepted, the planar ICT model is not ruled out because firm experimental evidence supports it. Among these it is the fact that some rigidized systems such as bicyclic 4-aminobenzonitrile derivatives exhibit dual fluorescence. We present here an ab initio CASSCF/CASPT2 study of a series of these compounds with the alicyclic chain ranging from 5 to 7 carbon atoms and compare their ICT mechanism with the more flexible 4-aminobenzonitrile (ABN) and 4-(dimethylamino)benzonitrile (DMABN). We present the energetics, geometries, and valence bond structures of the critical points of the potential-energy surfaces of the ground, local excited (LE), and ICT states. Our results show that the photophysical differences of the studied systems may be rationalized by two factors: the position of the ICT and LE potential-energy surfaces at the first stages of the ICT reaction and the relative energies of the excited-state minima. Computational evidence is presented that a twisted ICT structure can be adopted in some molecules such as NXC6 and NXC7 and that the anomalous band of the fluorescence spectra of these systems is emitted from a twisted ICT species.     

Low-birefringent, chiral banana phase below calamitic nematic and/or smectic C phases in oxadiazole derivatives

Bent-shaped molecules based on the oxadiazole central core with various side wings and terminal chain groups have been synthesized, and their liquid-crystalline behavior was investigated by optical microscopic, X-ray, and electrooptic measurements. These molecules exhibit liquid-crystal polymorphism including both the calamitic and banana phases. Such a characteristic polymorphism is attributable to the larger bend angle of the oxadiazole core compared to that of the resorcinol core used in conventional banana molecules. Only one type of banana phase, designated as the Bx phase, is formed. It appears upon cooling from the nematic and smectic liquid crystals and exhibits chiral domains with a very weak birefringence (apparently optically isotropic). By applying an electric field, the Bx phase is altered to a high-birefringence B2 phase with a homochiral SmC(A)P(A) structure that exhibits an antiferroelectric response. From detailed analyses of the optical texture and X-ray patterns through the transformation from well-oriented calamitic phases, the Bx phase was found to exhibit a helical structure, which arises as a frustration from the ground-state B2 phase in such a manner that the blocks of B2 layers are twisted with respect to each other in a direction parallel to the layer plane similarly to the twisted grain boundary (TGB) phase.