Electro-disclinic effect in tilted smectic phases of banana-shaped liquid crystal materials

We give the first evidence that the director tilt angle can be reduced by electric fields in the tilted smectic phase of banana-shaped molecules. In these phases the value of polarization is determined by the molecular packing and no electro-clinic effect is expected. Our studies show that high electric fields eventually induce a meta-stable phase with zero director tilt. The tilted phase slowly recovers at low fields. We propose that the field-induced quenching of the layer fluctuations is responsible for the observed effects.     

Classical and quantum mechanics of diatomic molecules in tilted fields

We investigate the classical and quantum mechanics of diatomic molecules in noncollinear (tilted) static electric and nonresonant linearly polarized laser fields. The classical diatomic in tilted fields is a nonintegrable system, and we study the phase space structure for physically relevant parameter regimes for the molecule KCl. While exhibiting low-energy (pendular) and high-energy (free-rotor) integrable limits, the rotor in tilted fields shows chaotic dynamics at intermediate energies, and the degree of classical chaos can be tuned by changing the tilt angle. We examine the quantum mechanics of rotors in tilted fields. Energy-level correlation diagrams are computed, and the presence of avoided crossings quantified by the study of nearest-neighbor spacing distributions as a function of energy and tilting angle. Finally, we examine the influence of classical periodic orbits on rotor wave functions. Many wave functions in the tilted field case are found to be highly nonseparable in spherical polar coordinates. Localization of wave functions in the vicinity of classical periodic orbits, both stable and unstable, is observed for many states.     

Direct smectic A-smectic C*A phase transition

The anticlinic smectic CA phase belongs to the class of tilted smectic phases with an azimuthal angle alternating from one direction (theta=0) to the other (theta=pi) in successive layers. It occurs in general at lower temperature than the uniformly tilted smectic C phase, but may be obtained directly from the untilted smectic A phase. We use the chiral nCTBB9* series synthesized in this laboratory, in order to obtain a phase transition as close as possible to second order, as revealed by DSC. We measure the temperature behaviour of the birefringence and of the optical rotatory power across the transition in order to characterize the tilt angle. We finally study the optical response to a periodic electric field which excites separately the smectic C* and C*A soft modes. The main conclusion is that the only order parameter governing the critica Al behaviour of the phase transition is the tilt angle theta, as we get common divergence of both soft modes at the same temperature. This confirms previous high resolution calorimetric studies by Ema et al. that saw in MHPOBC an initial mean-field second order phase transition when the tilt appears, followed by sharp first order restructuring transitions between the tilted subphases.     

Direct smectic A-smectic C*A phase transition

The anticlinic smectic CA phase belongs to the class of tilted smectic phases with an azimuthal angle alternating from one direction (theta=0) to the other (theta=pi) in successive layers. It occurs in general at lower temperature than the uniformly tilted smectic C phase, but may be obtained directly from the untilted smectic A phase. We use the chiral nCTBB9* series synthesized in this laboratory, in order to obtain a phase transition as close as possible to second order, as revealed by DSC. We measure the temperature behaviour of the birefringence and of the optical rotatory power across the transition in order to characterize the tilt angle. We finally study the optical response to a periodic electric field which excites separately the smectic C* and C*A soft modes. The main conclusion is that the only order parameter governing the critica Al behaviour of the phase transition is the tilt angle theta, as we get common divergence of both soft modes at the same temperature. This confirms previous high resolution calorimetric studies by Ema et al. that saw in MHPOBC an initial mean-field second order phase transition when the tilt appears, followed by sharp first order restructuring transitions between the tilted subphases.     

Nematic twist-bend phase under external constraints

ABSTRACT

The recently discovered twist-bend nematic phase, N_TB, has short-pitched heliconical structure with doubly degenerate handedness. In contrast to the classic nematic, in the N_TB phase the director is spontaneously distorted, resulting in unusual elastic properties. The response of the N_TB phase to external stimuli, like chiral doping or applied fields might provide further information about its structure and can find utilisation in practical applications. Here, the N_TB behaviour is theoretically investigated under chiral doping and strong electric fields. We show that the chiral doping removes the N_TB degeneration and modifies the conical tilt angle, leaving the pitch unchanged. Thus, the N_TB helical twisting power is very high and strongly non-linear. Under electric field, we consider separately the ferroelectric, flexoelectric and dielectric couplings. We show that the experiments reported so far disagree with the ferroelectric behaviour, indicating that the N_TB phase is not spontaneously polarised. On the contrary, the observed polar effects fit well with the flexoelectric coupling, confirming the degenerated heliconical structure of the phase. Under very strong fields, we predict a second-order twist-bend nematic – nematic phase transition due to the dielectric torque on the director.     

Light diffraction studies on director arrangement in the polymer‐pinned striped pattern obtained via the electric field‐induced Fréedericksz transition of nematics

We have observed an anomalous pattern forming phenomenon in which a striped pattern in a nematic liquid crystal appeared after removing an electric field following a Fréedericksz transition, and this pattern was preserved even in the equilibrium state in zero‐electric field. The nematic director arrangement in the striped pattern was investigated by light diffraction measurements. The stripes are proposed to consist of a periodic distortion of the nematic directors, specifically, tilted directors with the same absolute value of tilt angle but of opposite sign are alternately arrayed. The proposed model of the stripes is in good accord with the experimental results of light diffraction dependence on polarizing direction and light incidence angle.     

Two distinct modulated layer structures of an asymmetric bent-shape smectic liquid crystal

We present chemical synthesis, polarising optical microscopy, electric current, and small-angle X-ray scattering measurements on a strongly anisotropic bent-shape liquid crystal material. We find that it has two layer-undulated ferroelectric phases, M1 and M2. In the higher temperature M2 phase the undulation amplitude and period increases on cooling, similar to other published materials. It can be identified with a tilted modulated phase. In the M1 phase the molecular plane is not tilted, and – in sharp contrast with all prior observations – the modulation amplitude and period decrease on cooling. These observations can be explained with a ‘leaning’ director structure, where the leaning angle is decreasing on cooling.     

Graphene and liquid crystal mediated interactions

ABSTRACT

The two-dimensional graphene-honeycomb structure can interact with the liquid crystal’s (LC) benzene rings through π–π electron stacking. This LC–graphene interaction gives rise to a number of interesting physical and optical phenomena in the LC. In this paper, we present a combination of a review and original research of the exploration of novel themes of LC ordering at the nanoscale graphene surface and its macroscopic effects on the LC’s nematic and smectic phases. We show that monolayer graphene films impose planar alignment on the LC, creating pseudo-nematic domains (PNDs) at the surface of graphene. In a graphene-nematic suspension, these PNDs enhance the orientational order parameter, exhibiting a giant enhancement in the dielectric anisotropy of the LC. These anisotropic domains interact with the external electric field, resulting in a non-zero dielectric anisotropy in the isotropic phase as well. We also show that graphene flakes in an LC reduce the free ion concentration in the nematic media by an ion-trapping process. The reduction of mobile ions in the LC is found to have subsequent impacts on the LC’s rotational viscosity, allowing the nematic director to respond quicker on switching the electric field on and off. In a ferroelectric LC (smectic-C* phase), suspended graphene flakes enhance the spontaneous polarisation by improving the tilted smectic-C* ordering resulting from the π–π electron stacking. This effect accelerates the ferroelectric-switching phenomenon. Graphene can possess strain chirality due to a soft shear mode. This surface chirality of graphene can be transmitted into LC molecules exhibiting two types of chiral signatures in the LCs: an electroclinic effect (a polar tilt of the LC director perpendicular to, and linear in, an applied electric field) in the smectic-A phase, and a macroscopic helical twist of the LC director in the nematic phase. Finally, we show that a graphene-based LC cell can be fabricated without using any aligning layers and ITO electrodes. Graphene itself can be used as the electrodes as well as the aligning layers, obtaining an electro-optic effect of the LC inside the cell.     

Anchoring of a nematic liquid crystal on an anisotropic substrate

A nematic liquid crystal in contact with a flat solid substrate is studied by means of a mesoscopic Landau-de Gennes theory. It is assumed that the substrate is anisotropic, i.e. the directions x and y in the surface of the substrate are not equivalent, and the only symmetry is the mirror symmetry y ? - y. Assuming the simplest form of the bare surface free energy, where only the linear terms in the nematic order parameter are taken into account, we study anchoring directions induced by the interaction of the liquid crystal with the substrate. A phase diagram in terms of the surface fields and the temperature is obtained. Depending on the values of the surface fields we find four types of anchoring: the symmetric planar anchoring, with the director along x, the symmetric tilted anchoring, with the director in the xz plane, the antisymmetric planar anchoring, with the director along y, and the asymmetric tilted anchoring, with the director tilted with respect to all three axes.     

Horizontal chevron configurations in ferroelectric liquid crystal cells induced by high electric fields

Application of a high electric field to a S*_c ferroelectric liquid crystal cell may cause the formation of horizontal chevron configurations with the smectic layers tilted by the amount of the chevron angle (in the case of the present investigation equal to the director tilt angle) with respect to the normal to the rubbing direction of the cell substrates. The layer structure resembles that of the well-known vertical chevron configuration, but in the plane of the substrate instead of perpendicular to it, and is similar to that recently reported for the stripe-shaped texture. Between crossed polarizers, the two domain types appear to switch in opposite directions when an a.c. electric field is applied. The temperature dependence of the observation of horizontal chevron structures was investigated and an explanation is proposed analogous to that for the stripe texture model.     

Director distribution in field-induced undulated structures of cholesteric liquid crystals

Structures with a periodic in-plane liquid crystal director field modulation induced by an electric field are studied in cholesteric liquid crystals (CLCs). A phenomenon of the electric-field-induced instability in a planarly aligned cholesteric cell is used to create these undulated structures. The initial field-off state is planarly aligned with the cholesteric helix axis oriented perpendicular to the cell substrates. The interaction of the CLC with an electric field results in modulation of the refractive index, which is visualised as stripe domains oriented either along or perpendicular to the rubbing direction at cell alignment surfaces. The threshold electric field for the undulation appearance and a period of stripes are measured experimentally for three Grandjean zones (ratio d/p ~ 0.5, 1.0, and 1.5, where d is a cell thickness and p is the natural cholesteric pitch). For the zone with d/p ~ 1.0 using numerical simulations, we describe in detail the director distribution at an applied electric field. It is found that the in-plane undulated structure is characterised by a conical director rotation on moving along the alignment direction. The conical axis is tilted with respect to the alignment axis. The sign of the tilt angle depends on the handedness of CLC.     

The alignment of a liquid crystal in the smectic A phase in a high surface tilt cell

Liquid crystal alignment is studied using propagating optical mode techniques for a cell with a high surface tilt SiO alignment. The director configuration is determined for both the nematic and smectic A phases. In the nematic phase a uniform splay across the cell is demonstrated, as predicted by continuum theory. In the smectic A phase the structure is seen to be nearly uniform in the central region of the cell with large splay in boundary layers of about 0.5 μm thickness. The reason for this appears to be competition between the tilted surface alignment forces and internal forces within the bulk of the smectic A layer which would induce a homogeneous configuration.     

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal mixture

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic C_a* (SmC_a*) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmC_a* is about 20° larger than in SmA*. The large optical tilt (45°) in the SmC_a* phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations.     

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal mixture

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic C_a* (SmC_a*) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmC_a* is about 20° larger than in SmA*. The large optical tilt (45°) in the SmC_a* phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations.     

Electric-field driven director oscillations in a nematic liquid crystal: a NMR investigation

We have investigated the oscillatory behavior of the nematic director for 4-pentyl-4'-cyanobiphenyl (5CB) when it is subjected to a static magnetic field and a sinusoidal electric field. In these experiments the two fields were inclined at about 50 degrees and the frequency of the electric field was varied from several hertz to approximately 1000 Hz. The director orientation was measured using time-resolved deuterium NMR spectroscopy since this has the advantage of being able to determine the state of director alignment in the sample. In fact, for all of the frequencies studied the director is found to remain uniformly aligned. Since the diamagnetic and dielectric anisotropies are both positive the director oscillates in the plane formed by the two fields. These oscillations were observed to continue for many cycles, indicating that the coherence in the director orientation was not lost during this motion. The maximum and minimum angles made by the director with the magnetic field were determined, as a function of frequency, from the NMR spectrum averaged over many thousand cycles of the oscillations. At low frequencies (several hertz) these limiting angles are essentially independent of frequency but as the frequency increases the two angles approach each other and become equal at high frequencies, typically 1000 Hz. Our results are well explained by a hydrodynamic theory in which the sinusoidal time dependence of the electric field is included in the torque-balance equation. This analysis also shows that, for a range of frequencies between the high and low limits, these NMR experiments can give dynamic as well as static information concerning the nematic phase.     

Dynamics of the smectic layer reorientation of ferroelectric liquid crystals

Detailed experimental results of a systematic investigation of the dynamics of the in-plane smectic layer reorientation in SmC* ferroelectric liquid crystals on application of different types of asymmetric electric fields are reported. The reversible reorientation of smectic layers is characterized as a function of field asymmetry, electric field amplitude, frequency, cell gap and temperature. On the basis of the observed behaviour we discuss a phenomenological interpretation of the smectic layer reorientation in terms of dominant influences director switching, convection due to ionic motion and liquid crystal substrate interactions which limit the rotation to the amount of twice the tilt angle.     

Mechanism of nematic molecular alignment based on friction charges and surface topology by rubbing

A new and simple electric charge interaction mechanism has been proposed to explain the behaviour of the tilt angle of liquid crystals by rubbing. The mechanism of the molecular alignment is elucidated based on the effect of a static electric charge on a substrate surface treated by rubbing. An electric field which is dependent on the topology of a substrate surface allows a planar orientation of molecules with positive dielectric anisotropy. With increasing rubbing strength, the tilt angle varies slowly. The director of molecules with negative dielectric anisotropy is uniform and has a tilt angle determined by the molecular permanent dipole direction. The air-liquid crystal interface case is also considered. This model enables us to give a unified picture of the molecular alignment mechanism.     

Light-controlled reorientation of nematic liquid crystal driven by an electric field

The joint influence of optical and (quasi-)static electric fields on the orientation of liquid crystal gives rise to peculiar effects. In this article we report on the generation of transient domains in liquid crystals, which are an order of magnitude larger than the size of the optical field profile. The formation of such a domain is due to the fact that the initially present optical field reverses the pre-tilt, and the voltage that is then applied gives rise to an amplification of the tilt angle. The resulting reorientation of the director strongly depends on the starting conditions of the preliminary present optical field. We demonstrate different switching conditions, depending on the relation between the incident angle of the beam and the pre-tilt angle. The resulting refractive index profiles give rise to lensing effects.     

The orientational order parameters of a dendritic liquid crystal organo-siloxane tetrapode oligomer, determined using polarized infrared spectroscopy

The observed macroscopic anisotropic properties such as the components of infrared (IR) absorbances of liquid crystals are expressed in terms of the order parameters of the long molecular axis, molecular, and phase biaxiality. The order parameters of the organo-siloxane tetrapode liquid crystal of zero dendritic order (G0) in its nematic and smectic phases have been determined using results of the polarized IR spectroscopic measurements on a planar homogenously and hometropic aligned cells. The spatial components of the absorbances for the vibrational bands (in the mesogenic unit, terminal chains, and spacer) have been measured and analyzed. For the laboratory reference system, the apparent orientational order parameter S of the mesogen unit shows a significant drop in the transition from the nematic to the smectic phase while the phase biaxiality order parameter P increases to almost 0.4 in the smectic phase. This result shows that the director is tilted out of the sample plane in the smectic phase. The molecular biaxiality parameter D is found to be positive both for the nematic and smectic phases. This suggests that the carbonyl dipoles are oriented close to the tilt plane. For the vibrational bands in the chains, low values of S and D indicative of their low orientational order are obtained. As a result of the interaction among the molecules in the tilted smectic phases, the transition dipoles show positive correlations for the transversal and negative for the longitudinal dipoles.     

Manifestation of chiral asymmetry of ferroelectric liquid crystals induced by optically active dipole dopants in a linear electrooptic effect

The existence of eight combinations of absolute spatial configuration, helix handedness and handedness of director tilt has been shown for ferroelectric liquid crystals induced by optically active dipole dopants (optically active diesters of 4,4'-terphenyl dicarboxylic acid). As in the case of individual ferroelectrics alternation of the helix handedness is observed depending on absolute configuration of the C*-atom and its position relative to the rigid core of the molecule. However for these induced ferroelectric liquid crystals the helix handedness does not depend on the inductive effect of the substituent adjacent to the C* atom, e.g. the helix handedness of all the (S)-2-chlorine substituted materials coincides with that of the (S)-2-methyl-butyl derivative. Substitution of a chlorine atom by a cyano group followed by conversion of absolute spatial configuration of the C* atom results in the opposite helical sense. Thus asymmetric parameters of the induced ferroelectric liquid crystals helix handedness and the handedness of director tilt (or the sign of P_s) do not depend directly on the absolute configuration of C* atom and its position in a molecule. For the substances investigated within all of the temperature range of the induced smetic C* phase no reversal of the tilt direction handedness was observed.