Design, synthesis and characterization of a linear hydrogen bonded homologous series

A linear hydrogen bonded liquid crystalline homologous series has been synthesized and characterized. Hydrogen bond is formed between p-n-dodecyloxy benzoic acid and various p-n-alkyl benzoic acids whose alkyl chain vary from octyl to ethyl. Synthesized complexes are characterized by FTIR, ¹H NMR and ¹³C NMR studies for inferring the formation of hydrogen bonds. Polarizing Optical Microscopy (POM) and DSC studies reveal various mesophases and their corresponding transition temperatures along with respective enthalpy values. All the seven synthesized complexes exhibit rich liquid crystalline mesomorphism. A new phase namely smectic X has been observed in five of the complexes with a narrow thermal range. This phase has been characterized by optical textural, DSC, tilt angle and helicoidal pitch studies. Smectic X is sandwiched between traditional smectic C and re-entrant smectic C (designated as C_R) phases. Homeotropic transition in nematic phase is observed in all the mesogens and thus these materials can be used as thermally controlled optical shutters. Tilt angle in smectic C, smectic X and smectic C_R phases have been experimentally elucidated for all the mesogens.     

Thermal and optical characterization of a novel series of supramolecular liquid crystals

Supramolecular hydrogen bonded liquid crystal (SMHBLC) homologous series is synthesized and characterized. Hydrogen bond is formed between p-n-alkyloxy benzoic acids (nOBA, where n=7 to 12) and Iodo substituted benzoic acid (I_mBA) respectively. The isolated homologs are characterized by various techniques like Polarizing Optical Microscopy (POM), Differential Scanning Calorimetry (DSC), ¹H Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). From the POM and DSC studies phase diagram has been constructed and discussed. A new smectic ordering, labeled as smectic R, has been characterized which exhibits a ribbon like texture. This phase is observed in a complex pertaining to the undecyloxy carbon number. Tilt angle in smectic R phase and in traditional smectic C of all the complexes have been experimentally deduced and the results are fitted and so obtained β value concurrences with the Mean field theory predicted value.     

Design and characterization of hydrogen bonded ferroelectric liquid crystals: A study of light modulation in nematic and smectic orderings

A novel series of hydrogen bonded ferroelectric liquid crystals (HBFLC) have been isolated. Phase transition temperatures obtained by differential scanning calorimetry (DSC) and textural observations elicited by polarizing optical microscope (POM) studies are discussed. Phase diagram is constructed from the above data. Salient feature of the present work is observation of a light modulation due to field induced transitions (FiT) in nematic and smectic C* phases. Tilt angle measurements in various FiT of smectic C* phase are discussed. One of the mesogens in nematic phase behaves like an optical modulator; helical pitch measurements support the above observation.     

Design,synthesis and characterization of a linear hydrogen bonded homologous series exhibiting reentrant smectic C ordering

Design, synthesis and characterization of seven linear hydrogen bonded liquid crystal complexes derived from mesogenic p–n-decyloxy benzoic acid and p–n-alkyl benzoic acids designated as 10OØn (where n varied from ethyl to octyl) are reported. FTIR studies confirm the hydrogen bond formation in all these complexes. The phase transition temperatures and their corresponding enthalpy values are experimentally deduced from Differential Scanning Calorimetry (DSC) studies. POM and DSC data are further utilized for the construction of 10OØn phase diagram. Two Odd–even effects have been evinced, one in enthalpy values and the other in corresponding transition temperatures across the isotropic to nematic phase transition. An interesting result is the observation of re-entrant smectic ordering, designated as smectic C_R in three higher ordered mesogens. A new smectic ordering, smectic X, has been observed which is sandwiched between traditional smectic C and re-entrant smectic C_R. Magnitudes of optical tilt angle in smectic C, smectic X and smectic C_R are experimentally found to attain saturation with decrement of temperature in the corresponding phase. The occurrence of smectic X and smectic C_R are discussed with relation to the molecular chemical structure. The optical filtering action in smectic C and re-entrant smectic C_R phases have been analyzed.     

Synthesis,characterization and mesomorphic properties of new liquid-crystalline compounds involving ester–chalcone linkages

We report the synthesis and evaluation of thermal behaviour of two novel series of chalcone-based liquid-crystalline compounds. The flexibility in these systems is provided by attaching straight alkoxy chain at one end. All the mesogens have been characterized by spectroscopic methods such as ¹H-NMR, FTIR, mass spectra, UV/Vis, and also elemental analysis. Their thermal behaviour was evaluated mainly by polarizing optical microscopic observation and DSC studies. It has been observed that the majority of the compounds display nematic and/or smectic mesophases. In both the series, compounds having C₃ to C₇ tail display only enantiotropic nematic phase, whereas C₈ and C₁₀ homologues exhibit enantiotropic smectic C and nematic phases. The higher homologues with C₁₂, C₁₄ and C₁₆ tails show the smectic C phase only.     

Optical modulation in nematic phase of halogen substituted hydrogen bonded liquid crystals

A series of halogen-substituted hydrogen-bonded liquid crystalline complexes have been designed and synthesised. A successful attempt has been made to form complementary hydrogen bonding between the dodecyloxy benzoic acid (12BAO) and halogen-substituted benzoic acids and the physical properties exhibited by the individual complexes are studied. The complexes obtained are analysed by polarising optical microscope (POM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and dielectric studies. The formation of complementary hydrogen bond is confirmed through FTIR spectra. An interesting feature of this series is the observation of a field-induced transition (FiT) in nematic phase. Another interesting phenomenon is the observation of a new smectic X phase (worm-like texture) in all the synthesised complexes. Dielectric relaxation studies in the smectic C phase of these hydrogen bonded complexes along with the Arrhenius and the Cole–Cole plots are discussed. Optical tilt angle in smectic C phase and the corresponding fitted data analysis concur with the Mean field theory prediction.     

Phase transition behavior of hydrogen bonded liquid crystal (6BA)<Subscript>2</Subscript>-(BPy)<Subscript><Emphasis Type="Bold">x</Emphasis></Subscript> as studied by <Superscript>2</Superscript>H NMR

The thermal properties and the orientational order of hydrogen-bonded liquid crystals (6BA)₂-(BPy)_0.4 and (6BA)₂-(BPy)_0.3 (6BA: 4-n-hexylbenzoicacid, BPy: 4,4’-bipyridine) were investigated by DSC and ²H NMR. On cooling, isotropic liquid - liquid crystal phase transition temperatures were T _C= 409 and 405 K for (6BA)₂-(BPy)_0.4 and (6BA)₂-(BPy)_0.3, respectively. Thermal anomalies in the liquid crystal phase were observed at T _LC1= 402 and T _LC2= 375 K for (6BA)₂-(BPy)_0.4 and at T _LC1= 398 and T _LC2= 375 K for (6BA)₂-(BPy)_0.3. For (6BA)₂-(BPy)_0.4, only the smectic component was created above T _LC1. In addition, the nematic component was created below T _LC1. The nematic component gradually changed to the smectic component with decreasing temperature and only the smectic component was observed below T _LC2. For (6BA)₂-(BPy)_0.3, only the nematic component was created above T _LC2. The phase transition from the nematic phase to the smectic phase took place at around T _LC2.     

Theoretical investigation of antiferroelectric (SmCA) subphases by hydrodynamical approach

We provide a hydrodynamical approach utilizing time dependent Landau-Ginzburg model (L-G) and the Cahn-Hilliard model (C-H) to investigate antiferroelectric liquid crystals (AFLCs) exhibiting different chiral phases between paraelectric smectic A (SmA^?) phase and antiferroelectric smectic C_A^? phase (SmC_A^?). Introducing conserved and non-conserved order parameters in C-H and L-G models, we have predicted the appearance of a chiral smectic C (SmC^?) phase and a ferrielectric SmC_FI1^? phase (three layers SmC_A^?) in an antiferroelectric phase sequence. The three layers periodicity for SmC_FI1^? phase is studied in detail with a non-uniform layer interactions among smectic layers with strong experimental support. Finally, we provide some theoretical basis for the non-uniformity of our proposed layer interactions.     

Thermal and Optical Properties of Some Hydrogen-Bonded Liquid Crystal Mixtures

Phase transition properties of the mixtures of hydrogen-bonded nematic liquid crystals (HBLC) 4-hexylbenzoic acid (6BA), 4-(octyloxy)benzoic acid (8OBA), and 4-(decyloxy)benzoic acid (10OBA) have been investigated by means of differential scanning calorimetry (DSC) and polarize optic microscope (POM). The DSC and POM results clearly indicate the existence of smectic and nematic phase transitions in binary mixtures. The phase transition temperature values of 6BA/10OBA mixtures have clearly increased with increasing heating rate. The activation energies were calculated for the phase transitions of 6BA/10OBA liquid crystal (LC) mixture. The optical transmittance of these mixed hydrogen-bonded nematic liquid crystals was investigated in terms of temperature variations through electrooptic methods. The electrooptic experiments indicate that, while low in the nematic phase, the optical transmittance is very high at the nematic-isotropic phase transition. The transmitted light intensity values of 6BA/8OBA mixture are somewhat higher than those of other binary mixtures, 6BA/10OBA and 8OBA/10OBA, a result associated with the different alkyloxy chain lengths.     

Heterotic Toda fields

A non-left-right symmetric conformal integrable Toda field theory is constructed. It is found that the conformal algebra for this model is the product of a left chiral W_r+1 algebra and a right chiral W_r+1² algebra. The general classical solution is constructed out of the chiral vectors satisfying the so-called classical exchange algebra. In addition, we derived an explicit Wronskian type solution in relation to the constrained WZNW theory. We also showed that the A_∞ limit of this model is precisely the (B₂, C₁) flow of the standard Toda lattice hierarchy.     

Temperature scaling of ferroelectric hysteresis in hard lead zirconate titanate bulk ceramic

The temperature scaling of the ferroelectric hysteresis was investigated in hard lead zirconate titanate (PZT) bulk ceramic. The power-law temperature scaling relations were obtained for hystersis area 〈A〉, remnant polarization P_r, and coercivity E_C in the forms of 〈A〉∝T^-0.9650, P_r∝T^-0.0261, and E_C∝T^-0.8823, respectively, which are mostly comparable to those of its soft counterpart. The observation that P_r decayed more slowly with temperature than in soft PZT was attributed to the presence of the complex defects in hard PZT. However, the product of P_r and E_C still provided the similar scaling law on the T dependence in comparison with 〈A〉. PACS 77.80.-e; 77.80.Fm; 77.84.-s; 77.84.Dy     

Deep level transient spectroscopy (DLTS) study of defects introduced in antimony doped Ge by 2 MeV proton irradiation

Deep level transient spectroscopy (DLTS) and Laplace-DLTS have been used to investigate the defects created in Sb doped Ge after irradiation with 2 MeV protons having a fluence of 1×10¹³ protons/cm². The results show that proton irradiation resulted in primary hole traps at E_V +0.15 and E_V +0.30 eV and electron traps at E_C ?0.38, E_C ?0.32, E_C ?0.31, E_C ?0.22, E_C ?0.20, E_C ?0.17, E_C ?0.15 and E_C ?0.04 eV. Defects observed in this study are compared with those introduced in similar samples after MeV electron irradiation reported earlier. E_C ?0.31, E_C ?0.17 and E_C ?0.04, and E_V +0.15 eV were not observed previously in similar samples after high energy irradiation. Results from this study suggest that although similar defects are introduced by electron and proton irradiation, traps introduced by the latter are dose dependent.     

Electric field distribution and effective nonlinear AC and DC responses of graded cylindrical composites

The perturbation method is used to study the localization of electric field distribution and the effective nonlinear response of graded composites under an external alternating-current (AC) and direct-current (DC) electric field E_app = E₀ (1+sin ωt). The dielectric profile of the cylindrical inclusions is modeled by function ε_i (r) = C_k r^k (r ≤ a), where r is the radius of the cylindrical inclusion, and C_k, k, a are parameters. In the dilute limit, the local potentials and the effective nonlinear responses at all harmonics are derived. Meanwhile, the general effective nonlinear responses are also derived and compared with the effective nonlinear responses at harmonics under the AC and DC external field. It is found that the effective nonlinear AC and DC responses at harmonics can be calculated by those of the general effective nonlinear of the graded composites under the external DC electric field. Moreover, the obtained local electrical fields show that the electrical field distribution in the cylindrical inclusions is controllable, and the maximum of the electric field inside the cylinder is at its center.     

Optical measurements of phase transitions in difluorophenylazophenyl benzoate thermotropic liquid crystal with specific orientated fluorine atoms

Phase transition temperature and optical properties of the special oriented fluorine atoms in difluorophenylazophenyl Benzoate Thermotropic Liquid Crystal nominated (III) were studied and measured. Absorbance and transmittance in the visible region at room temperature for the compound III dissolved in methylene chloride of different concentrations were determined. The maximum absorbance for the compound III was in the blue region (447?nm) and the molar absorption coefficient was found to be 0.93 (L. mMol^?1.cm^?1). The transition temperature was determined for the thermotropic LC compound III by using DSC, POM and modified spectrophotometer techniques. Nematic and smectic phases during the cooling process were observed. Ordinary and extraordinary refractive indices, birefringence, order parameter and the molecular polarizability were determined with different temperatures for the LC phases of compound III.     

Material tensor parameters of LiNbO3 relevant for electro- and elasto-optics

The complete set of self-consistent parameters of nominally undoped LiNbO₃ crystals of congruent composition that describe the electro-optic, piezoelectric, elasto-optic, elastic, and dielectric response has been determined by numerically evaluating available measurements. The parameters were determined at room temperature and consist of the low-frequency clamped dielectric constants ε^S _ij, elastic stiffness constants at constant electric field C^E _ijkl, piezoelectric stress coefficients e_ijk, elasto-optic constants at constant electric field p^E _ijkl, and clamped electro-optic coefficients r^S _ijk. It is shown that the complete set is required for calculating the effective electro-optic coefficients and dielectric constants in photorefractive applications of LiNbO₃. Received: 4 January 2002 / Revised version: 1 February 2002 / Published online: 14 March 2002     

Optical shuttering action in nematic phase of SMHBLC: observation of a ribbon-like texture

In this study, complexes belonging to supramolecular hydrogen-bonded liquid crystal homologous series are synthesized and characterized. Hydrogen bond is formed between p-n-alkyloxy benzoic acids (nBAO, where n?=?5–11) and chlorobenzoic acid (ClBAO), respectively. The isolated homologues are characterized by various techniques such as polarizing optical microscopic (POM) studies, differential scanning calorimetry (DSC), and Fourier transform–infrared spectroscopy. Based on the POM and DSC studies, the phase diagram has been constructed and discussed. A new smectic ordering, labeled as smectic R, has been characterized, which exhibits a ribbon-like texture. This phase is observed in the complexes pertaining to the higher homologous series. Tilt angle in this phase has been experimentally deduced and the results are fitted to the power law which concurs with the mean-field theory predicted value. Optical shuttering action in the homologue has been detected in the nematic phase and the results are also discussed.     

Synthesis and mesomorphic properties of novel three-armed star-shaped mesogens of phloroglucinol (1,3,5-trihydroxybenzene) containing Schiff-base moiety

A series of symmetrical three-armed star-shaped mesogens based on phloroglucinol (1,3,5-trihydroxybenzene) as a core unit containing (4-benzylidene-substituted-aniline-4′-oxy)-6-bromohexane as peripheral arm where the 4-position at one end consisting different terminal substituent, X (X?=?fluoro, chloro, bromo, iodo and ethyl) was synthesized and characterized. The chemical structure of the title compounds were studied using FT-IR, ¹H- and ¹³C-NMR while their thermal behavior and mesomorphic properties were investigated via differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The results indicate that the three-armed compounds containing F, Cl, Br, and C₂H₅ substituents exhibit mesophase except for the analog having iodo substituent which is found to be non-mesogenic. The absence of liquid crystalline properties for iodo-substituted analog could be due to the influence of the substituent of which the lamellar packing of these compounds will be disrupted when the size of substituent is increased.     

Phase polymorphism and electro-optical properties of a ferroelectric liquid crystal containing the biphenyl system

ABSTRACT

In this article we present results concerning phase transitions and physical properties of the ferroelectric phase of the compound (S)-4-(1-methylheptyloxy)biphenyl–4'-(heptyloxy phenyl)-4-carboxylate (MHOBOPO7). The compound has the following phases: smectic ferroelectric C (SmC*), chiral nematic N*, and two defected phases, TGB_C and blue phase. The mesomorphic properties were investigated by means of three complementary methods: differential scanning calorimetry, polarizing light optical microscopy, and transmitted light intensity. The electro-optical measurements were carried out on an ordered sample in a middle electric field during very slow cooling from the nematic phase to the ferroelectric phase.     

Measurements of absolute values of electrooptic coefficients in a ferroelectric liquid crystal

Weak external electric field E causes two effects in chiral smectic liquid crystals: linear change of the optic axis direction and modification of the shape of the indicatrix. The relative changes in the light intensity consist of two components. The first component represents the modulation with the fundamental frequency f and the second one, with the doubled frequency 2f (second harmonic). We carried out measurements of the electrooptic modulation at both the first and second harmonics frequency. The applied calibration procedure allowed for expressing the experimental results as angular quantities independent of experimental conditions. Therefore we were able to determine the absolute values of the coefficients describing both effects of the electric field on the optical properties of the sample. We studied the temperature dependence of the first and second order coefficients in the ferroelectric smectic C? and paraelectric smectic A phases. The experiments delivered an information on the structure of tilted smectic liquid crystals and its dependence on the electric field.     

Compact variational wave functions for bound states in three-electron atomic systems

The variational procedure to construct compact and accurate wave functions for three-electron atoms and ions is developed. The procedure is based on the use of six-dimensional Gaussoids written in the relative four-body coordinates r ₁₂, r ₁₃, r ₂₃, r ₁₄, r ₂₄, and r ₃₄. The nonlinear parameters in each basis function have been carefully optimized. Using these variational wave functions, we have determined the energies and other bound state properties for the ground 1² S-states in a number of three-electron atoms and ions. The three-electron atomic systems considered in this work include the neutral Li atom and nine positively charged lithiumlike ions: Be⁺, B²⁺, C³⁺, ..., Na⁸⁺, and Mg⁹⁺. Our variational wave functions are used to determine the hyperfine structure splitting and field shifts for some lithium-like ions. The explicit formulas of the Q ⁻¹ expansion are derived for the total energies of these three-electron systems. The article is published in the original.