Short range order in the isotropic phase of antiferroelectric liquid crystals

Optical activity measurements in the isotropic phase of two antiferroelectric liquid crystal systems in which the chirality can be varied reveal unusual behaviour of the short range order. In one system the phase sequence as the chirality is increased is smectic A, smectic C^* _A, and smectic Q. In the other system the phase sequence is smectic C^*, smectic C^* _A, and smectic Q as the chirality is increased. The short range order of the isotropic phase behaves similarly for these systems, showing mean field behaviour at low chirality and far above the phase transition, but deviating from this behaviour significantly as the chirality is increased and the phase transition is approached. These optical activity results indicate how different is the short range order in the isotropic phase for these antiferroelectric liquid crystal systems and demonstrates the crucial role played by chirality. Past theoretical work that includes smecticlike fluctuations in the calculation of short range order in the isotropic phase is capable of qualitatively explaining these results.     

Short range order in the isotropic phase of antiferroelectric liquid crystals

Optical activity measurements in the isotropic phase of two antiferroelectric liquid crystal systems in which the chirality can be varied reveal unusual behaviour of the short range order. In one system the phase sequence as the chirality is increased is smectic A, smectic C^*_A, and smectic Q. In the other system the phase sequence is smectic C^*, smectic C^*_A, and smectic Q as the chirality is increased. The short range order of the isotropic phase behaves similarly for these systems, showing mean field behaviour at low chirality and far above the phase transition, but deviating from this behaviour significantly as the chirality is increased and the phase transition is approached. These optical activity results indicate how different is the short range order in the isotropic phase for these antiferroelectric liquid crystal systems and demonstrates the crucial role played by chirality. Past theoretical work that includes smecticlike fluctuations in the calculation of short range order in the isotropic phase is capable of qualitatively explaining these results.     

The new high tilt mixtures with antiferroelectric phase at a broad temperature range and a long helical pitch

Five new bicomponent eutectic mixtures based on compounds different in the bridge between a rigid core and a chiral centre (-COO- or -CH₂O-) or in the optical purity (‘S’ or racemic ‘R,S’) were prepared and characterised. Their mesomorphic properties were tested by means of polarising optical microscopy and differential scanning calorimetry. The helical pitch of prepared mixtures was estimated with selective reflection method. The optical tilt angle Θ of mixtures was also measured and discussed.     

A new mesogenic mixture with antiferroelectric phase only at a broad temperature range

New compounds (S)-4?-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[3-(2,2,3,3,4,4,5,5,5-nonafluoropentyloxy)prop-1-oxy]benzoates were synthesised and characterised. Their mesomorphic properties were tested by means of polarising optical microscopy and differential scanning calorimetry. The multicomponent antiferroelectric high tilt mixture with long pitch has been also formulated and characterised. The helical pitch of prepared mixture was estimated with selective reflection method.     

New AFLC: a trimesogen presenting antiferroelectric smectic C phase (SmCA) and twist grain boundary smectic A phase (TGBA)

A first oligomeric antiferroelectric liquid crystal, a cyclohexane based trimesogen, was synthesized. It was characterized by microscopic observation, differential scanning calorimetry, helical pitch measurement, X-ray diffraction and electro-optical study. A large domain of antiferroelectric phase (DeltaT 55 C) and a very rich polymorphism (SmC*, SmC*, SmC* , A FI SmC*, TGBA, BP) are exhibited by the trimesogen.     

Nano-segregated structures of hydrogen-bonded mesogens with perfluorinated moieties: cubic phase formation and first order smectic A to smectic C phase transition

Two series of mesogenic compounds having both a perfluorinated substituent and a hydrogen bonding active site were synthesized and their phase behavior investigated. Due to the chemical architecture of these materials exhibiting amphiphilic character, structures of nano-segregation are expected to form. We found a thermotropic cubic phase with Ia3d symmetry in one of the acid/base hydrogen-bonded complexes, which is a nano-segregated structure. Moreover materials exhibiting a first order smectic A to smectic C phase transition were found, which was ascertained by differential scanning calorimetry measuring a large latent heat, and X-ray diffraction experiments observing abrupt changes of physical properties at the phase transition, i.e. the tilt angle, the intensity and the half-width of the small angle reflection. This first order phase transition occurs due to the frustration of nano-segregated structures of lamellar phases.     

Nano-segregated structures of hydrogen-bonded mesogens with perfluorinated moieties: cubic phase formation and first order smectic A to smectic C phase transition

Two series of mesogenic compounds having both a perfluorinated substituent and a hydrogen bonding active site were synthesized and their phase behavior investigated. Due to the chemical architecture of these materials exhibiting amphiphilic character, structures of nano-segregation are expected to form. We found a thermotropic cubic phase with Ia3d symmetry in one of the acid/base hydrogen-bonded complexes, which is a nano-segregated structure. Moreover materials exhibiting a first order smectic A to smectic C phase transition were found, which was ascertained by differential scanning calorimetry measuring a large latent heat, and X-ray diffraction experiments observing abrupt changes of physical properties at the phase transition, i.e. the tilt angle, the intensity and the half-width of the small angle reflection. This first order phase transition occurs due to the frustration of nano-segregated structures of lamellar phases.     

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.     

Electrical driving of the surface memorization in dimerized nematics with short range smectic order

Electrical control of the surface memorization of an oriented smectic C texture in the temperature range of dimerized nematics with short range smectic C order (4-n-alkyloxybenzoic acids) is presented. It is demonstrated that by suitable choice of the electric field parameters and surface conditions it is possible to separate the thermal and electrical components of the total erasure activation energy. The significant role of the double charge electric layer in the mechanism of the surface memorization is verified. By the electrical control of the memorization, we have confirmed the electrical part of the modified Rapini-Papoular anchoring energy in the effective surface energy.     

On the phase sequence of antiferroelectric liquid crystals and its relation to orientational and translational order

The substance MHPOBC is the oldest and still most important reference antiferroelectric liquid crystal (AFLC). There is still considerable controversy concerning the correct phase designations for this material and, in particular, about the presence or absence of SmC* in its phase sequence. By means of dielectric spectroscopy and polarizing microscopy, we show that whereas the pure compound lacks the SmC* phase, this phase rapidly replaces the SmC*_β subphase through the reduced purity resulting from temperature-induced chemical degradation which is hard to avoid under standard experimental conditions. X-ray investigations furthermore show that this change in phase sequence is coupled to a decrease in translational order. This explains the large variations in the reported phase sequence and electro-optic behaviour of MHPOBC, in particular concerning the SmC*β phase which has been said to exhibit ferro-, ferri- as well as antiferroelectric properties. It is likely that the sensitivity of the AFLC phase sequence to sample purity is a general property of AFLC materials. We discuss the importance of optical and chemical purity as well as tilt and spontaneous polarization for the observed phase sequence and propose that one of the key features determining the existence of the different tilted structures is the antagonism between orientational (nematic) and translational (smectic) order. The decreased smectic order (increased layer interdigitation) imposed by chemical impurities promotes the synclinic SmC* phase at the cost of the AFLC phases SmC*_α, SmC*_β, SmC*_γ and SmC*_a. We also propose that the SmA* phase in FLC and AFLC materials may actually have a somewhat different character and, depending on its microstructure, some of the tilted phases can be expected to appear or not to appear in the phase sequence. AFLC materials exhibiting a direct SmA* -SmC*_a transition are found to be typical ‘de Vries smectics’, with very high orientational disorder in the SmA* phase. Finally, we discuss the fact that SmC*_β and SmC*_γ have two superposed helical superstructures and explain the observation that the handedness of the large scale helix may very well change sign, while the handedness on the unit cell level is preserved.     

A bilayer model of the double hysteresis loop in antiferroelectric liquid crystals

We investigate, both analytically and numerically, a simple model of the field induced double hysteresis loop in AFLC materials. This bilayer model of the bulk of an AFLC describes the free energy in terms of polar and non-polar interactions due to surface alignment, the electric field/dipole interaction in each layer and the dipole/dipole interaction between the layers. The static hysteresis loop is found analytically and the stability of each analytic solution is investigated. The dynamic switching characteristics are found numerically and then investigated as the system parameters and electric field characteristics are changed.     

Stochastic model for the reorientation of molecules around their long axes in a smectic C phase

In smectic phases molecules can reorientate around their long and short axes. The motion of a molecule around its long axis is non-cooperative and influenced by both stochastic and deterministic forces exerted by neighbouring molecules. Solving the Smoluchovsky equation for such a reorientation process, two-time correlation functions are calculated which are related to frequency-dependent susceptibilities. The results are used for investigating how deterministic forces in higher ordered smectic phases have an effect on microwave spectra. It can be concluded that the quadrupolar ordering produces a splitting of the relaxation frequency. This splitting, which should occur at the transition from the smectic A to the smectic C phase, is only weakly influenced by an additional dipolar (ferroelectric) ordering.     

Amphiphilic taper-shaped oligomer exhibiting a monolayer smectic A to columnar phase transition

We prepared two series of liquid-crystalline oligomers composed of phenylpyrimidine based mesogenic cores, alkyl spacers and semiperfluorinated alkyl chains in one series and only alkyl chains in the second series. Their physical properties were investigated using optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. The oligomers possessing a semiperfluorinated alkyl chain show a phase sequence of SmC–SmA–Col when the number of phenylpyrimidine moieties was increased. The compound possessing three phenylpyrimidine cores was found to exhibit monolayer SmA and Col phases. On the other hand, the oligomer composed of an alkyl chain and three phenylpyrimidine cores showed only a nematic phase. We discuss effects of the shape amphiphilicity and the hydrocarbon–fluorocarbon amphiphilicity on phase transition behaviour of the amphiphilic oligomers.     

Studies of the higher order smectic phase of the large electroclinic effect material W317

Abstract

We present studies of the large electroclinic effect material W317. We found via X-ray scattering, calorimetry and optical observation that quenching from the smectic A* phase results in several higher order phases including an orthogonal (hexatic) smectic with short range in-layer translational order and no interlayer order. We characterize the electroclinic response in the quenched phase, and determine its magnitude and response time as a function of electric field amplitude and temperature.     

The influence of lateral substituents on the occurrence of a transition between two polar smectic phases with antiferroelectric properties

The synthesis and mesomorphic properties of two homologous series of bent-core (BC) compounds derived from 2,7-dihydroxynaphthalene are reported. The two series differ from one another by an electron-withdrawing or an electron-donating lateral substituent on the middle phenyl ring of the arms of the BC. Very interestingly, contrasting results are obtained in which polar phases are observed in compounds containing a chloro substituent and apolar smectic C and nematic phases are obtained when this substituent is replaced by a methyl group. The mesophases have been characterised by using a combination of polarised light optical microscopy, differential scanning calorimetry, X-ray diffraction measurements, electro-optical and dielectric studies.     

Textural transformations of a smectic phase with asymmetric banana-shaped molecules

Materials consisting of asymmetric banana-shaped molecules may form a smectic C_G phase having C₁ symmetry. We have studied textural transformations in a smectic phase of an asymmetric chlorine-substituted banana-shaped material under electric and mechanical fields. We observed two novel features that have not been observed so far on corresponding materials with symmetric banana-shaped molecules. These observations, however, could be explained by the same arguments as were used for the symmetric molecules. Although our studies do not exclude the possibility that the material has C₁ symmetry, we suggest that the chlorine molecules are positioned arbitrarily and the bulk has C₂ symmetry.     

Textural transformations of a smectic phase with asymmetric banana-shaped molecules

Materials consisting of asymmetric banana-shaped molecules may form a smectic C_G phase having C₁ symmetry. We have studied textural transformations in a smectic phase of an asymmetric chlorine-substituted banana-shaped material under electric and mechanical fields. We observed two novel features that have not been observed so far on corresponding materials with symmetric banana-shaped molecules. These observations, however, could be explained by the same arguments as were used for the symmetric molecules. Although our studies do not exclude the possibility that the material has C₁ symmetry, we suggest that the chlorine molecules are positioned arbitrarily and the bulk has C₂ symmetry.     

Multivariable kinetic theory of the first order phase transitions

The problem of calculation of the steady state homogeneous nucleation rate in the multidimensional space of the variables describing a nucleus is considered. Within the framework of the theory proposed, expressions for the nucleation rate and the steady state distribution function of nuclei are derived. The expression for the nucleation rate is invariant with respect to the space dimensionality and, in particular, involves the result of the one-dimensional theory. The distribution function is obtained in the initial, physical variables. In connection with the analysis of restrictions on the current direction, the question of symmetry of the matrix of diffusivities is considered; on the basis of the detailed balance principle it is shown that this matrix is symmetric. The question of normalizing the equilibrium distribution functions is investigated and the physical picture of the equilibrium state is described. The procedure of reducing the multidimensional theory to the one-dimensional one is described.     

Nature of smectic A*-C* phase transitions in a series of ferroelectric liquid crystals with little smectic layer shrinkage

The smectic layer spacing of two homologous series of ferroelectric liquid crystal compounds was characterized by small-angle x-ray diffraction and different degrees of smectic layer shrinkage on cooling from the SmA* into the SmC* phase were observed. The smectic A*-smectic C* phase transition was further studied by measuring the thermal and electric field effects on the optical tilt angle and the electric polarization. With decreasing length of the alkyl terminal chain the phase transition changes from tricritical exhibiting high layer shrinkage to a pure second-order transition with almost no layer shrinkage. This is explained by the increased one-dimensional translational order of the smectic layers, which seems to promote the "de Vries"-type [Mol. Cryst. Liq. Cryst. 41, 27 (1977)] smectic A*-C* phase transition with no or little layer shrinkage.     

Order-disorder antiferroelectric phase transition in a hybrid inorganic-organic framework with the perovskite architecture

[(CH3)2NH2]Zn(HCOO)3, 1, adopts a structure that is analogous to that of a traditional perovskite, ABX3, with A = [(CH3)2NH2], B = Zn, and X = HCOO. The hydrogen atoms of the dimethyl ammonium cation, which hydrogen bond to oxygen atoms of the formate framework, are disordered at room temperature. X-ray powder diffraction, dielectric constant, and specific heat data show that 1 undergoes an order-disorder phase transition on cooling below 156 K. We present evidence that this is a classical paraelectric to antiferroelectric phase transition that is driven by ordering of the hydrogen atoms. This sort of electrical ordering associated with order-disorder phase transition is unprecedented in hybrid frameworks and opens up an exciting new direction in rational synthetic strategies to create extended hybrid networks for applications in ferroic-related fields.