Effects of anisotropy,order parameter,and viscosity on translational self-diffusion in nematic liquid crystals

A theory developed for the translational diffusion in nematic liquids crystals shows a dependence on the viscosities, order parameter, and molecular structure. Theoretical results for self-diffusion in p-azoxyanisole at 125°C are D^{∥ = 4.3 × 10?6, D⊥ = 3.1 × 10?6 c2/s}, andD^∥/D^⊥ = 1.4.     

Dimension of mesogenic molecules as atomic clusters

The problem regarding the mass dimension D of mesogenic molecules as atomic clusters is formulated and solved using computer simulation and analytical calculations. For a large number of compounds belonging to different chemical classes, it is shown that the cores of discotic lacunar (rodlike, lathlike) molecules forming nematic or columnar discotic (calamitic) phases have a fractional dimension 1 < D _c < 2 (D _c ≈ 1). The dependences of the dimension D _c on the symmetry, the conformation, and the structural-chemical features of the molecular core are determined. It is demonstrated that, in the region of side flexible chains in molecules of both types, the dimension D _ch can be either smaller or larger than unity, depending on the chain conformation. An analytical expression accounting for the results of numerical experiments is obtained for the dimension D _ch .     

Landau theory of long-range orientational order

The most general quartic Landau free energies are constructed for orientational order parameters which transform like L = 2, 4, and 6 irreducible representations of SO(3). In each case a complete phase diagram is determined using group theoretical techniques in conjunction with the linear programming method. The accessible low-symmetry phases for L = 6 representation are D_∞, Y, O, and D₆. For L = 4 they are D_∞, O, and D₄. D_∞ is accessible for L = 2. In the cases L = 6 and 4 it is found that the phase diagram is dominated by the icosahedral and octahedral symmetries, respectively. The bond densities in the low-symmetry phases are also analyzed.     

Correlation of the molecular structure of discotic nematic liquid crystals with their orientational order and specific features of the nematic-isotropic phase transition

The orientational order parameter S of molecules in high-temperature discotic nematic liquid-crystal phases of triphenylene derivatives is investigated as a function of the length of side flexible molecular chains at different temperatures. It is established that the orientational order parameters S in the range of the transition from the nematic phase to the isotropic liquid phase (the N _D -I transition) are smaller than those predicted from the molecular-statistical theory and computer simulation. It is shown that the N _D -I transition is close to both the isolated Landau point and the tricritical point (regardless of the chemical structure of the molecules and the anisotropy of dispersion intermolecular interactions). Consistent explanations are offered for a number of experimental findings, such as the anomalously small changes in the enthalpy and entropy upon the N _D -I transition (as compared to those revealed upon the N-I transition in calamitic nematic liquid crystals), the anomalously strong response of the isotropic phase of discotic nematic liquid crystals to external fields (thermodynamically conjugate to the order parameter S) and the long relaxation times of this response, and the formation of cybotactic discotic molecular clusters in the isotropic phase in the vicinity of the N _D -I transition.     

Macroscopic behavior of non-polar tetrahedratic nematic liquid crystals

We discuss the symmetry properties and the macroscopic behavior of a nematic liquid crystal phase with D_2d symmetry. Such a phase is a prime candidate for nematic phases made from banana-shaped molecules where the usual quadrupolar order coexists with octupolar (tetrahedratic) order. The resulting nematic phase is nonpolar. While this phase could resemble the classic D _∞h nematic in the polarizing microscope, it has many static as well as reversible and irreversible properties unknown to nonpolar nematics without octupolar order. In particular, there is a linear gradient term in the free energy that selects parity leading to ambidextrously helical ground states when the molecules are achiral. In addition, there are static and irreversible coupling terms of a type only met otherwise in macroscopically chiral liquid crystals, e.g. the ambidextrous analogues of Lehmann-type effects known from cholesteric liquid crystals. We also discuss the role of hydrodynamic rotations about the nematic director. For example, we show how strong external fields could alter the D_2d symmetry, and describe the non-hydrodynamic aspects of the dynamics, if the two order structures, the nematic and the tetrahedratic one, rotate relative to each other. Finally, we discuss certain nonlinear aspects of the dynamics related to the non-commutativity of three-dimensional finite rotations as well as other structural nonlinear hydrodynamic effects.     

Specific features of photoisomerization of provitamin D 3 in a nematic liquid crystal

Photoisomerization of provitamin D ₃ (7-dehydrocholesterol) in a nematic liquid crystal (ZLI-1695, Merck) is investigated in detail by UV absorption spectroscopy. It is found that dissolution of chiral molecules of provitamin D ₃ induces the cholesteric phase in a nematic. The spectral kinetics of photoisomerization in this phase changes significantly from that in an ethanol solution. A sharp nonmonotonic dependence of the increase in accumulation of trans isomer tachysterol in a liquid crystal matrix with a decrease in the induced cholesteric pitch from 2200 to 25 μm is revealed.     

The elusive thermotropic biaxial nematic phase in rigid bent-core molecules

The biaxial nematic liquid crystalline phase was predicted several decades ago. Several vigorous attempts to find it in various systems resulted in mis-identifications. The results of X-ray diffraction and optical texture studies of the phases exhibited by rigid bent-core molecules derived from 2,5-bis-(p-hydroxyphenyl)-l,3,4-oxadiazole reveal that the biaxial nematic phase is formed by three compounds of this type. X-ray diffraction studies reveal that the nematic phase of these compounds has the achiral symmetry D_2h, in which the overall long axes of the molecules are oriented parallel to each other to define the major axis of the biaxial phase. The apex of the bent-cores defines the minor axis of this phase along which the planes containing the bent-cores of neighboring molecules are oriented parallel to each other.     

Stability,elastic properties and electronic structures of L12-ZrAl3 and D022-ZrAl3 up to 40 GPa

The effects of high pressures on structure stability, elastic properties and electronic structures of zirconium trialuminide L1₂- and D0₂₂-ZrAl₃ compounds have been investigated by first-principles calculations within the local density approximation. The equilibrium structure and formation energy show that L1₂-ZrAl₃ is more stable than D0₂₂-ZrAl₃ at the applied pressure. The elastic properties and Debye temperatures of (L1₂, D0₂₂)-ZrAl₃ increase with the increasing pressure and the calculated values in the ground state are in good agreement with the available experiment data. The mechanical anisotropic properties were discussed using the universal anisotropic index A^U. The sound velocities along the [100], [110] and [111] directions were also calculated for both phases. The calculated electronic properties under high pressures suggest that the decreased electronic density of states (DOS) at the Fermi level and the changed charges distribution lead to the observed decrease of the structural stability for (L1₂, D0₂₂)-ZrAl₃ under high pressures.     

Diffusion in thermotropic liquid crystals

Diffusion coefficients in mesophases of thermotropic liquid crystals have been measured to a considerable extent only during the last twelve years. Some theories on diffusion in mesophases have been developed too. Measurements in nematic, smectic A, smectic B, and smectic C mesophases have been carried out by mass transport techniques, detected by radio-tracers or optically, by NMR spin-echo techniques, and by quasi-elastic neutron scattering. The diffusion is anisotropic in most of the cases. In nematics self-diffusion parallel to the molecular director (D₆) is somewhat faster than perpendicular (D_⊥). Both diffusion coefficients show about the same activation energy. Impurity diffusion (small molecules dissolved in mesophases) demonstrates the same behaviour with less anisotropy. In smectics A and C the diffusion coefficients D₆ and D_⊥ can be nearly equal. The anisotropy is now shown in their respective activation energies with E₆>E_⊥. This effect is more pronounced in impurity than in self-diffusion. In addition impurity diffusion shows a strong anisotropy of the diffusion coefficients (D_⊥?D₆). In smectics B the activation energies E₆ and E_⊥ of self-diffusion seem again to be equal and the diffusion coefficients show a small anisotropy (D_⊥≥D₆).     

Proton and deuteron magnetic resonance of methanes,silanes and GeH3D dissolved in nematic liquid crystals

The proton and deuteron magnetic resonance spectra of CH₄, CH₃D, CH₂D₂, CHD₃, CD₄, SiH₄, SiH₃D, SiH₂D₂, SiH₃D, SiD₄, GeH₃D, dissolved in nematic liquid crystals, are reported. It was found that these molecules, which are essentially tetrahedral, exhibit anisotropic interactions and are partially oriented in the nematic phase. This effect is presumably due to slight deformations induced by the anisotropic medium. Some of the aspects related to the interpretation of the results are discussed.     

Estimation of effective Debye temperature from sound velocity of N-(p-n-alkoxybenzylidene)-p-n-alkylanilines, (nO.m) liquid crystalline compounds

The ratio of specific heats (γ), Poisson's ratio (σ), effective Debye temperature (θ_D) collision factor (S_m), etc., are estimated in different LC phases of N-(p-n-alkoxybenzylidene)-p-n-alkylanilines, (nO.m's) liquid crystalline compounds using the density and sound velocity data. The variation of these parameters in different mesomorphic phases with the chain length is studied. The effective Debye temperature (θ_D), the collision factor (S_m) exhibits a similar variation with the alkyl chain length. Further, the space filling factor (r_fm) estimated using Kittel's formula is constant for all the materials irrespective of the phase with a value of 0.416. The molecular radius shows an increment of 0.074, 0.072 and 0.068 ? per CH₂ group in isotropic, nematic and smectic-A phases respectively in 5O.m series. Further, the specific heat ratio (γ) value is found to be lower in isotropic phase than in liquid crystalline phases. The data is compared with the body of the data in the literature.     

Orientational order parameter studies in two symmetric dimeric liquid crystals – an optical study

The optical technique developed by [W. Kuczynski, B. Zywucki, and J. Malecki, Determination of orientational order parameter in various liquid-crystalline phases, Mol. Cryst. Liq. Cryst. 381 (2002), pp. 1–19; B.J. Zywucki and W. Kuczynski, IEEE transactions on optical phenomena – The orientational order in nematic liquid crystals from birefringence measurements, Dielectr. Electr. Insul. 8 (2001), pp. 512–515] is fabricated and used to determine the orientational order parameter in two dimeric liquid crystalline compounds nematic and SmA phases of α,ω-bis(4-alkylanilinebenzylidene-4′-oxy)alkane (m.OnO.m) homologous series. The compounds studied are 5.O8O.5 and 5.O10O.5 which exhibit nematic and SmA, and nematic phases, respectively. The orientational order parameter in both the phases of nematic and SmA phases of the compound one and the nematic phase of the compound two are obtained using the principle of Newton's rings which gives directly the birefringence, δn of the liquid crystal dimer. The merits of the technique used are presented over the conventional techniques for the determination of orientational order parameter. The results for the two compounds are compared with those values estimated from n _e, n _o and density using the two internal field models due to Vuks and Neugebauer applicable to nematic phase.     

Bulk diffusion in the undamped Frenkel-Kontorova model

We present new simulation results for the undamped Frenkel-Kontorova model. These support the existence of the bulk diffusion coefficient D, which has been called into question by earlier simulation work of Schneider and Stoll. We point out that D can be studied by three independent routes, and we show that these all provide evidence for the existence of D and yield the same numerical value for it in the particular thermodynamic state examined.     

Dynamic phase transitions and dynamic phase diagrams in the kinetic spin-5/2 Blume-Capel model in an oscillating external magnetic field: Effective-field theory and the Glauber-type stochastic dynamics approach

Using an effective field theory with correlations, we study a kinetic spin-5/2 Blume-Capel model with bilinear exchange interaction and single-ion crystal field on a square lattice. The effective-field dynamic equation is derived by employing the Glauber transition rates. First, the phases in the kinetic system are obtained by solving this dynamic equation. Then, the thermal behavior of the dynamic magnetization, the hysteresis loop area and correlation are investigated in order to characterize the nature of the dynamic transitions and to obtain dynamic phase transition temperatures. Finally, we present the phase diagrams in two planes, namely (T/zJ, h₀/zJ) and (T/zJ, D/zJ), where T absolute temperature, h₀, the amplitude of the oscillating field, D, crystal field interaction or single-ion anisotropy constant and z denotes the nearest-neighbor sites of the central site. The phase diagrams exhibit four fundamental phases and ten mixed phases which are composed of binary, ternary and tetrad combination of fundamental phases, depending on the crystal field interaction parameter. Moreover, the phase diagrams contain a dynamic tricritical point (T), a double critical end point (B), a multicritical point (A) and zero-temperature critical point (Z).     

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.     

Self-diffusion coefficient of nematic liquid crystals from diffusion concentration gradient

A dynamic study of the mass transport by optical methods provides a new approach to evaluate the nematic self-diffusion coefficient. This value is obtained by extrapolation to C = 0 in an empirical relation D_C = D₀ exp (-βC), where D_C is the mass-corrected impurity diffusion coefficient and C is the local concentration of the diffusion profile.     

Detecting columnar deformations in a supermesogenic octapode by proton NMR relaxometry

We used proton ( ¹H nuclear magnetic relaxation (NMR) dispersions to study the molecular dynamics in the isotropic phase and mesophases (nematic and columnar hexagonal) of a supermesogenic octapode formed by laterally connecting calamitic mesogens to an inorganic silsesquioxane cube through flexible spacers. The dispersions of the spin-lattice relaxation time (T₁) are interpreted through relaxation mechanisms used for the study of molecular dynamics in low-molar-mass liquid crystals but adapted to the case of liquid crystalline supermolecules. At high frequencies (above 10MHz) the behaviour of the T₁ with the Larmor frequency is similar for all phases and is ascribed to local reorientations and/or rotations. At intermediate and low frequencies (below 10MHz) our results show notable differences in the T₁ behaviour with respect to the mesophases. The nematic (N) and isotropic (Iso) phases’ low-frequency results are similar and are interpreted for both phases in terms of order director fluctuations (ODF), revealing that even in the isotropic phase local nematic order is detected by proton NMR relaxometry. Local nematic order in the Iso phase is interpreted in terms of the presence of nematic cybotactic clusters induced by the interdigitation of mesogens that is promoted by the silsesquioxane octapode molecular structure. In the columnar hexagonal (Col _h phase, the T₁ dispersions show that elastic columnar deformations (ECD) dominate the nuclear magnetic relaxation below 10MHz. This result shows that the columnar packing of the octapode clearly restricts the collective fluctuations of the mesogenic units inspite of their local nematic order.     

Proton NMR study of pure liquid crystal exhibiting re-entrant phase transition

Proton NMR experiment was carried out on a pure re-entrant nematic liquid crystal OBBC in nematic (N), smectic A(S_A), and re-entrant nematic (RN) phases. The re-entrant phase transition was detected by measuring the rotation pattern (θ₀-dependence) of the spectra in the external field. The dipolar splitting at θ₀=0 showed smooth temperature-dependence through the phase changes, RN?S_A?N. Orientational order of the molecular core is thus hardly affected by the formation of 1-D density modulation. The temperature-dependence of the spin-lattice relaxation rate showed that translational self-diffusion is the predominant mechanism of relaxation in RN, but the director fluctuation is quite significant in N.     

IR Absorption and Raman spectroscopic study of reentrant-nematic liquid crystalline N-[4-(4-Octyloxy-benzoyloxy) Benzylidene]-4-Cyanoaniline (OBBC)

Abstract

The IR absorption and Raman scattering of OBBC have been investigated in the solid, ReN, SmA and nematic phases. The intensity of the 2229 cm^?1 band assigned to the C[tbnd]N stretching mode decreases with increasing temperature in the reentrant nematic phase; this is attributed to a change in the overlap of the molecules. While the IR bands at 1728 and 841 cm^?1 also show a remarkable temperature dependence, Raman bands do not show significant temperature dependence in the liquid-crystal phases.