The characteristic dielectric behaviour in ferroelectric liquid crystals at a phase transition and the contribution of the soft mode

The characteristic dielectric behaviour of ferroelectric liquid crystals with a large spontaneous polarization has been studied as functions of the D.C. bias field, frequency, cell thickness and applied pressure. Under the condition in which the contribution of the Goldstone mode is suppressed, a sharp peak in the temperature dependence of the dielectric constant is clearly observed at the transition between S_A and S*_C phases T _{S C *s A}. The relaxation of the soft mode is observed both in the S_A and S*_C phases by eliminating the contribution of the Goldstone mode under a D.C. bias field. Another relaxation is also observed in the S*_C phase around several kHz in addition to that of the soft mode and the Goldstone mode. The pressure effect on the soft mode was also studied.     

Dielectric and optical studies near the chiral smectic C-smectic A transition of (S)-2-hydroxy-4-decyloxybenzylidene-4'-amino-2p'-methylbutylcinnamate

The complex dielectric permittivity of HDOBAMBC has been measured in the vicinity of the chiral smectic C-smectic A transition as a function of temperature and frequency. The Goldstone mode contribution has been clearly identified and its relaxation frequency has been determined over the whole S*_C range. High accuracy tilt angle measurements have also been performed by using a new method which allows its determination in a direct and virtually continuous way. These experimental results together with additional measurements of the polarization and helical pitch have been compared with those of DOBAMBC and analized in the framework of the generalized Landau theory. As for DOBAMBC a reentrant behaviour S*_C-S_C-S*_C has been observed under an electric field near the S*_C-S_A transition.     

Circular dichroism in ferroelectric and antiferroelectric liquid crystals

Liquid crystal induced circular dichroism (LCICD) measurements were made to investigate the pretransitional phenomena in the S_A phase just above the S_A-S*_C and S_A-S*_CA phase transitions of both the first and the second order. The pretransitional LCICD in S_A was observed in the second order phase transition to S*_c and S*_cA, suggesting the existence of a dynamic helical structure in S_A. Such behaviour disappears when the transition is of the first order. It seems that the handedness of the dynamic helix in S_A is the same as that in S*_c even when the lower temperature phase is S*_cA. This is explained as a result of a dominant contribution of ferroelectric soft mode.     

Molecular dynamics study of the ferroelectric liquid crystal CI IPNOC by proton spin-lattice relaxation

Proton spin-lattice relaxation studies were carried out in the S_A and S*_C phases of the liquid crystal CI IPNOC using both conventional and fast field cycling NMR techniques. T₁ dispersion curves were obtained at two different temperatures for each mesophase covering frequencies from 10² to 3 × 10⁸ Hz. In both mesophases the T₁ data can be described assuming the presence of three different relaxation mechanisms, namely local molecular rotations, molecular self-diffusion and collective motions. The self-diffusion constant D₁ was evaluated for several temperatures and the activation energy associated with the diffusion process was obtained. The expected contribution of the soft-mode for the spin-lattice relaxation could not be separated from the contribution of other collective motions. The correlation times associated with the rotations around the molecular long axis and with the fluctuations of this axis were evaluated for both the S_A and the S*_C phases.     

Dielectric spectroscopy of an antiferroelectric liquid crystal showing an antiferroelectric-ferrielectric transition

We report the dielectric relaxation behaviour in the antiferroelectric SmC_A* and ferrielectric SmC_γ* phases of the antiferroelectric liquid crystal 4-[5-(4-octloxyphenyl)-2-pyrimidinyl]phenyl 4,4,4-trifluoro-3-(methoxyphenyl)butanoate which shows an antiferroelectric transition at around 88±0.1°C. In the SmC_A* phase, two dielectric relaxation modes have been found, namely the usual antiferroelectric Goldstone mode and another arising from molecular rotation around its short axis. In the SmC_γ* phase, one dielectric relaxation mode has been observed due to the ferrielectric Goldstone mode. Dielectric increments and relaxation frequencies of the antiferroelectric and ferrielectric phases are estimated from the fits of the Cole-Cole function of the dielectric spectrum. The dependence of the bias field in the ferrielectric phase is also discussed.     

Dielectric studies of different phases of a thin-layered ferroelectric liquid crystal with a small pitch and high spontaneous polarization

Dielectric spectroscopy of a ferroelectric liquid crystal with planar texture in the frequency range 100 Hz to 1 MHz has been carried out as a function of temperature from 25°C to 60°C at different DC fields varying from 0 to 12 kVcm^-1. From the measured dielectric strengths and relaxation frequencies, it is observed that the material has a S_c*-S_A* transition at 56·1°C and a S_A*-I transition at 58°C. The data of the S_c* phase have been assigned to the Goldstone mode. The rotational viscosity and elastic constant have been calculated from the observed data. The capacitance shows an abrupt drop at the critical DC field where unwinding of the helix occurs. The measured value of the critical field decreases with temperature and agrees to literature data from electrooptical experiments. On applying a DC field greater than 6·5 kV cm^-1 at room temperature, the liquid crystal shows the unwound S_c* and S_A* phases.     

Experimental and theoretical study of the influence of a bias electric field on the dielectric properties of the chiral smectic A* phase

The influence of a bias electric field on the temperature and frequency dependence of the soft mode part of the complex dielectric constant of the chiral smectic A* phase has been studied experimentally. It was found that only close to T_S*CS*A does the bias field have any influence on the experimentally determined quantities. Here the relaxation frequency increased with increasing bias field, while the corresponding dielectric strength decreases. We also present a theoretical calculation of the influence of a bias field on the complex dielectric constant of the chiral smectic A* phase which, apart from minor details, is in accordance with the observed behaviour. Finally we discuss how the nature of the electroclinic effect can be correlated with the influence of the bias field on the smectic A* dielectric constant.     

Microscopic organization of molecules in smectic A and chiral (racemic) smectic C phases: Dynamic molecular deformation effect on the SA to SC* (SC) transition

We investigated the correlation between orientational order and microscopic organization of the molecules in smectic A and chiral (racemic) smectic C phases by means of solid-state C-13 NMR, powder X-ray diffraction, and electrooptical measurements. The compounds under investigation are 4-((S)-2-methyloctanoyl)phenyl 4'-nonylbiphenyl-4-carboxylate ((S)-MONBIC) and its corresponding racemic compound ((S, R)-MONBIC). Static C-13 NMR indicates that: (1) the orientational angle of the tail with respect to the magnetic field decreases slightly both in the S_A and S*_C phases as decreasing temperature, and (2) the angle of the core with respect to the field decreases in the S_A phase but increases in the S*_C phase as decreasing temperature. Analysis of C-13 T₁ reveals that the dynamic molecular deformation for the core part can occur near the transition. We discuss the dynamic molecular deformation in comparison with the reorientation of the director at the S_A to S*_C transition. Based on the experimental results, we propose the structural model in which describes the microscopic organization of the molecules in the mesophases.     

Electroclinic effect near a smectic A-chiral smectic I transition

The electroclinic effect in the S_A phase of (S) (4'-decyloxy-2'-hydroxybenzylidene)-4-amino(1-ethoxycarbonylethyl) cinnamate has been studied. The induced tilt angles have been measured as a function of temperature near the S_A-S*_I transition at 87°C. The response of the material to different voltages and frequencies has been analysed by using two complementary optical techniques. At low A.C. probe fields the amplitude of the induced tilt shows a relaxational behaviour which can be described by a single relaxation time. The relaxation frequencies have been found to be linear in temperature near the transition, in a similar way to the S_A-S*_C transition.     

Dielectric studies of a ferroelectric liquid crystal

Measurements of the complex dielectric permittivity in the frequency range 30 Hz-13MHz have been made for the chiral smectic C and smectic A phases of the mixture ZLI-3654. In the S*_C phase a large contribution to the electric permittivity coming from the Goldstone mode was found. For the pretransitional region S*_C-S_A, only the soft mode has been detected. It is found that the molecular relaxation originating from the reorientation around the short axis is well separated from the soft mode even in the pretransitional region. The influence of different relaxation modes on the dielectric anisotropy is presented.     

The existence of four dielectric modes in the planar oriented S*c phase of a fluorinated substance

Abstract

Soft mode and Goldstone mode properties have been studied for a fluorinated substance. The dielectric spectra have been measured on the planar oriented samples, in the frequency range from 10 Hz to 10 MHz. The thickness of the sample was 10 μm and two kinds of capacitors were used: (i) a low resistance EHC cell and (ii) gold coated electrodes. A bias field up to 10kV cm^?1 has been applied to show the existence of both the soft mode and domain mode in the S*_c phase below T _c. In the S*_c phase a strong Goldstone mode has been observed with a low critical frequency (v ^G _C = 15 Hz). The high frequency side at the Goldstone mode spectrum is accompanied by a shoulder which consists of the soft mode and domain mode as well. In the vicinity of the S*_A-S*_C transition the dielectric parameters of the soft mode obey a Curie-Weiss law. The slope ratio is equal to ?1·62 for the inverse of dielectric increments (Δ∈^?1) and ?1·73 for the critical frequencies (v _c) obtained by using gold electrodes. The respective values received for the EHC cell are ?4·14 and ?2·1. The dielectric parameters of the domain mode have been obtained versus temperature and bias field. We can qualitatively show that a high frequency molecular relaxation is present in the S*_A and S*_C phases as the high frequency limit of dielectric permittivity is distinctly higher than the refractive index squared.     

Hindered reorientation of chiral molecules around their long axes in the S*C phase

In this work, the high frequency dielectric relaxation process has been studied for the N*, S*_A and S*_C phases of the mixture ZLI 3654. To this end, time domain spectroscopy (TDS) was used to cover the frequency range from 10⁷ to 10¹⁰ Hz. The dielectric parameters obtained show that the high frequency spectrum is mostly influenced by the reorientation of molecules around their long axes. In addition, the latter process seems to be strongly hindered in the S*_C phase, because the necessary relaxation time is of the order of 1 ns, whereas for the N* and S*_A phases, the relaxation time is remarkably shorter and equal to 0.3 and 0.4 ns, respectively.     

Dielectric spectroscopy of an antiferroelectric liquid crystal showing an antiferroelectric–ferrielectric transition

We report the dielectric relaxation behaviour in the antiferroelectric SmC_A* and ferrielectric SmC_γ* phases of the antiferroelectric liquid crystal 4-[5-(4-octloxyphenyl)-2-pyrimidinyl]phenyl 4,4,4-trifluoro-3-(methoxyphenyl)butanoate which shows an antiferroelectric transition at around 88±0.1°C. In the SmC_A* phase, two dielectric relaxation modes have been found, namely the usual antiferroelectric Goldstone mode and another arising from molecular rotation around its short axis. In the SmC_γ* phase, one dielectric relaxation mode has been observed due to the ferrielectric Goldstone mode. Dielectric increments and relaxation frequencies of the antiferroelectric and ferrielectric phases are estimated from the fits of the Cole–Cole function of the dielectric spectrum. The dependence of the bias field in the ferrielectric phase is also discussed.     

Dielectric spectroscopy of a smectic liquid crystal

Complex dielectric spectroscopy (frequency range 5 Hz–13 MHz) has been used to analyse the frequency, temperature and bias‐field dependences of the molecular dynamics of a very high‐spontaneous‐polarization ferroelectric liquid crystalline material exhibiting SmA, SmC* and unknown SmX smectic phases. Different smectic phase transition temperatures have been observed from the study of the temperature dependence of the dielectric strength and the relaxation frequency. The phase transition temperatures (crystalline to isotropic phases) have also been described very accurately from the temperature‐dependent symmetric and asymmetric shape parameters of the relaxation function and also the dc conductivity. In a planar aligned cell, two symmetric modes (Goldstone mode and domain mode) have been observed in both the SmX and SmC* phases. One asymmetric mode (X‐mode) observed in the SmC* and SmA phases could be related to the interaction of dipoles of the ferroelectric liquid crystals being affected by the surface of the cell. The soft mode, which usually appears very close to the SmC*–SmA phase transition was not observed until the bias field was applied. The second order nature of the SmC*–SmA phase transition was revealed.     

Dielectric properties of four room temperature ferroelectric and antiferroelectric multi-component liquid crystalline mixtures

Dielectric properties of four recently formulated room temperature multi-component liquid crystalline mixtures with paraelectric (SmA*), ferroelectric (SmC*) and antiferroelectric (SmC*_A) phases have been studied as a function of temperature and frequency. Under planer anchoring condition, dielectric spectroscopy revealed all the characteristic modes: low frequency P_L and high frequency P_H mode in SmC*_A phase, Goldstone mode (GM) in SmC* phase and soft mode (SM) in SmA* phase. Dielectric behaviour has also been studied under the application of DC bias electric field. With bias electric field, we have been able to study the soft mode dielectric behaviour in the SmC* phase. An unknown high frequency mode (X-mode) with and without bias is also observed in SmC* phase. Dielectric results are explained in the light of generalised Landau theory. The mixtures show very high soft mode electroclinic coefficient in the SmA* phase in addition to fast switching in SmC*_A and SmC* phases [30].     

Collective and molecular processes in a new class of ferroelectric liquid crystals

Electro-optic and dielectric studies have been performed for a thioester (with a chiral chain incorporating the lactic acid ester moiety), which exhibits a monotropic room temperature ferroelectric S_c* phase. Moreover, there are some hints that this substance also shows the recently discovered helicoidal S_A* phase. The dielectric and electro-optic measurements have been carried out using ITO coated glass plates (d = 10 μm). Planar alignment was obtained by means of an AC electric field (v = 1Hz and V_p-p = 70V). The tilt angle and spontaneous polarization temperature dependences show that the S_A*-S_c* transition is of second order. Soft mode behaviour in the pretransitional region also confirms this result. The monotropic S_c* phase exhibits a rather strong Goldstone mode (GM) with pronounced temperature dependence of the dielectric parameters. The molecular reorientation about the long axis has been found for both principal alignments. The homeotropic effective alignment was obtained by applying a magnetic field of 1-2 T to a thick sample (c. 100μm) placed in a specially designed cell for anisotropic high frequency measurements. The reorientation about the long axis gives a broad spectrum centred at c. 100MHz. This spectrum shows minor changes at the S_A*-S_c* transition.     

Re-entrant and induced mesophases: Mixed systems showing re-entrant TGBA and re-entrant cholesteric phases

We have investigated the behaviour of chiral carbohydrate-based trioxadecalines with a cyano group in mixed systems. The mixture of a trioxadecaline having a Ch phase and a trioxadecaline having a Ch, S_A and a S*_Cphase sequence induces a re-entrant TGB_A and Ch phase. Below the stabilized S*_C phase, a re-entrant Ch phase is observed. In the mixture of the cholesteric trioxadecaline with CCH7, itself only showing a nematic phase, a TGB_A phase and a broad range S_A phase are induced from two non-smectic compounds. Both mixtures show a blue phase with a pitch ranging from the UV to red depending on the molar fraction.     

Dielectric spectroscopy of a smectic liquid crystal

Complex dielectric spectroscopy (frequency range 5 Hz-13 MHz) has been used to analyse the frequency, temperature and bias-field dependences of the molecular dynamics of a very high-spontaneous-polarization ferroelectric liquid crystalline material exhibiting SmA, SmC* and unknown SmX smectic phases. Different smectic phase transition temperatures have been observed from the study of the temperature dependence of the dielectric strength and the relaxation frequency. The phase transition temperatures (crystalline to isotropic phases) have also been described very accurately from the temperature-dependent symmetric and asymmetric shape parameters of the relaxation function and also the dc conductivity. In a planar aligned cell, two symmetric modes (Goldstone mode and domain mode) have been observed in both the SmX and SmC* phases. One asymmetric mode (X-mode) observed in the SmC* and SmA phases could be related to the interaction of dipoles of the ferroelectric liquid crystals being affected by the surface of the cell. The soft mode, which usually appears very close to the SmC*-SmA phase transition was not observed until the bias field was applied. The second order nature of the SmC*-SmA phase transition was revealed.     

Collective fluctuation in chiral smectic phases of main-chain liquid crystalline polymers

We have investigated the collective fluctuation in the chiral smectic phases of main-chain polyesters having a mesogenic p,p'-dibenzoate unit via dielectric and dynamic electrooptical measurements. A relaxation due to the Goldstone mode was observed at several tens of Hz in the chiral smectic C (SmC*) phase in both measurements, where another relaxation associated with the soft mode was also confirmed around the SmA-SmC* phase transition temperature. Although the mesogens are linked together in a main-chain liquid crystalline polymer, the observed soft mode is associated with the tilt fluctuation of the average direction of the mesogens.     

Novel fluorinated liquid crystals. II. The synthesis and phase transitions of a novel type of ferroelectric liquid crystals containing 1,4-tetrafluorophenylene moiety

4-[(S)-2-Methylbutoxycarbonyl]phenyl 4-[(4-n-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl]benzoates have been prepared from the starting material 1-pentafluorophenyl-2-trimethylsilylacetylene. Polarizing microscope textural observation and DSC measurements of the phase transitions of these novel compounds showed that they were liquid crystals with chiral smectic C phase (S*_C), smectic A(S_A) and cholesteric (Ch) phases. The effects of the alkoxy chain length on the transition temperatures and enthalpies were also studied.