Ferroelectric molecule

Lahiri T, Pal Majumder T (2012) The effect of cross-linked chains of polymer network on the memory states of polymer stabilized ferroelectric molecules. Polymer 53 2121-2127 Lee K, Suh SW, Lee SD (1994a) Fast linear electro-optical switching properties of polymer-dispersed ferroelectric liquid crystals. Appl Phys Lett 64 718 Lee K, Suh SW, Lee SD, Kim CY (1994b) Ferroelectric response of polymer-dispersed chiral smectic C liquid crystal composites. J Korean Phys Soc 27(1) 86... 

As witli tlie nematic phase, a chiral version of tlie smectic C phase has been observed and is denoted SniC. In tliis phase, tlie director rotates around tlie cone generated by tlie tilt angle [9,32]. This phase is helielectric, i.e. tlie spontaneous polarization induced by dipolar ordering (transverse to tlie molecular long axis) rotates around a helix. However, if tlie helix is unwound by external forces such as surface interactions, or electric fields or by compensating tlie pitch in a mixture, so tliat it becomes infinite, tlie phase becomes ferroelectric. This is tlie basis of ferroelectric liquid crystal displays (section C2.2.4.4). If tliere is an alternation in polarization direction between layers tlie phase can be ferrielectric or antiferroelectric. A smectic A phase foniied by chiral molecules is sometimes denoted SiiiA, altliough, due to the untilted symmetry of tlie phase, it is not itself chiral. This notation is strictly incorrect because tlie asterisk should be used to indicate the chirality of tlie phase and not tliat of tlie constituent molecules. 

Chiral Smectic. In much the same way as a chiral compound forms the chiral nematic phase instead of the nematic phase, a compound with a chiral center forms a chiral smectic C phase rather than a smectic C phase. In a chiral smectic CHquid crystal, the angle the director is tilted away from the normal to the layers is constant, but the direction of the tilt rotates around the layer normal in going from one layer to the next. This is shown in Figure 10. The distance over which the director rotates completely around the layer normal is called the pitch, and can be as small as 250 nm and as large as desired. If the molecule contains a permanent dipole moment transverse to the long molecular axis, then the chiral smectic phase is ferroelectric. Therefore a device utilizing this phase can be intrinsically bistable, paving the way for important appHcations. 

Licjuid Crystals. Ferroelectric Hquid crystals have been appHed to LCD (Uquid crystal display) because of their quick response (239). Ferroelectric Hquid crystals have chiral components in their molecules, some of which are derived from amino acids (240). Concentrated solutions (10—30%) of a-helix poly(amino acid)s show a lyotropic cholesteric Hquid crystalline phase, and poly(glutamic acid ester) films display a thermotropic phase (241). Their practical appHcations have not been deterrnined. 

Other more exotic types of calamitic liquid crystal molecules include those having chiral components. This molecular modification leads to the formation of chiral nematic phases in which the director adopts a natural helical twist which may range from sub-micron to macroscopic length scales. Chirality coupled with smectic ordering may also lead to the formation of ferroelectric phases [20]. 

In the operation of ferroelectric liquid crystal devices, the applied electric field couples directly to the spontaneous polarisation Ps and response times depend on the magnitude E Ps. Depending on the electronic structure (magnitude and direction of the dipole moment as well as position and polarity of the chiral species) and ordering of the molecules P can vary over several orders of magnitude (3 to 1.2 x 10 ), giving response times in the range 1-100 ps. 

Zareba et al. [165] described the crystal structure of the chiral 4-(l-methyl-heptyloxycarbonyl)-phenyl 4-heptyloxytolane-4 -carboxylate (C7-tolane) which shows monotropic antiferroelectric and ferroelectric phases. The single-crystal X-ray analysis of this compound shows that the crystal has a smectic-like layer structure composed of largely bent molecules where the chain of the chiral group is almost perpendicular (86°) to the core moiety. Within the layers, the molecules are tilted. The central tolane group of the molecule is roughly planar. 

Stimulated by these observations, Odelius et al. [73] performed molecular dynamic (MD) simulations of water adsorption at the surface of muscovite mica. They found that at monolayer coverage, water forms a fully connected two-dimensional hydrogen-bonded network in epitaxy with the mica lattice, which is stable at room temperature. A model of the calculated structure is shown in Figure 26. The icelike monolayer (actually a warped molecular bilayer) corresponds to what we have called phase-I. The model is in line with the observed hexagonal shape of the boundaries between phase-I and phase-II. Another result of the MD simulations is that no free OH bonds stick out of the surface and that on average the dipole moment of the water molecules points downward toward the surface, giving a ferroelectric character to the water bilayer. 

In Science, every concept, question, conclusion, experimental result, method, theory or relationship is always open to reexamination. Molecules do exist Nevertheless, there are serious questions about precise definition. Some of these questions lie at the foundations of modem physics, and some involve states of aggregation or extreme conditions such as intense radiation fields or the region of the continuum. There are some molecular properties that are definable only within limits, for example, the geometrical stmcture of non-rigid molecules, properties consistent with the uncertainty principle, or those limited by the negleet of quantum-field, relativistic or other effects. And there are properties which depend specifically on a state of aggregation, such as superconductivity, ferroelectric (and anti), ferromagnetic (and anti), superfluidity, excitons. polarons, etc. Thus, any molecular definition may need to be extended in a more complex situation. 

When the mesogenic compounds are chiral (or when chiral molecules are added as dopants) chiral mesophases can be produced, characterized by helical ordering of the constituent molecules in the mesophase. The chiral nematic phase is also called cholesteric, taken from its first observation in a cholesteryl derivative more than one century ago. These chiral structures have reduced symmetry, which can lead to a variety of interesting physical properties such as thermocromism, ferroelectricity, and so on. 

Mclnnes EJL (2006) Spectroscopy of Single-Molecule Magnets. 122 69-102 Merunka D, Rakvin B (2007) Anharmonic and Quantum Effects in KDP-Type Ferroelectrics Modified Strong Dipole-Proton Coupling Model. 124 149-198 Meshri DT, see Singh RP (2007) 125 35-83... 

Here we focus on the effect of dipolar dispersion laws for high-frequency collective vibrations on the shift and width of their spectral line, with surface molecules inclined at an arbitrary angle 6 to the surface-normal direction. For definiteness, we consider the case of a triangular lattice and the ferroelectric ordering of dipole moments inherent in this lattice type.56,109 Lateral interactions of dynamic dipole moments p = pe (e = (sin os, sin6fcin , cos )) corresponding to collective vibrations on a simple two-dimensional lattice of adsorbed molecules cause these vibrations to collectivize in accordance with the dispersion law 121... 

The earliest approach to explain tubule formation was developed by de Gen-nes.168 He pointed out that, in a bilayer membrane of chiral molecules in the Lp/ phase, symmetry allows the material to have a net electric dipole moment in the bilayer plane, like a chiral smectic-C liquid crystal.169 In other words, the material is ferroelectric, with a spontaneous electrostatic polarization P per unit area in the bilayer plane, perpendicular to the axis of molecular tilt. (Note that this argument depends on the chirality of the molecules, but it does not depend on the chiral elastic properties of the membrane. For that reason, we discuss it in this section, rather than with the chiral elastic models in the following sections.)... 

It was quickly recognized that chirality would play an important role in discotic liquid crystals, not only for the possibility of creating cholesteric and ferroelectric liquid crystals but also as a tool for studying the self-assembly of these molecules as a whole, both in solution and in the solid state. However, initial studies revealed that expression of chirality in discotic liquid crystals was not as straightforward as for liquid crystals derived from calamitic molecules. More recently, with the increase in interest in self-assembly and molecular recognition, considerably more attention has been directed to the study of chiral discotics and their assemblies in solution. The objective of this chapter is... 

To understand how chirality is expressed, it is important to first describe the different thermotropic mesophase assemblies which can be formed by chiral discotics. Even though expression of chirality has been observed in thermotropic mesophases, the chiral expression occurs in a rather uncontrolled manner, and systems which are suitable for applications, for example, easily switchable columns/ferroelectric discotic liquid crystals, consequently have not yet been developed. Hence, the assembly of discotics in solution has received considerable attention. Supramolecular assemblies of discotic molecules in solution are still in their infancy and have not yet found commercial application, but they are of fundamental importance since they allow a detailed and focused investigation of the specific interactions that are required to express chirality at higher levels of organization. As such, the fundamental knowledge acquired from supramolecular assemblies in solution might formulate the design criteria for thermotropic chiral discotic mesophases and provide the necessary tools for the creation of functional systems. 

This situation changed dramatically in 1996 with the discovery of strong electro-optic (EO) activity in smectics composed of bent-core, bowshaped, or banana-shaped achiral molecules.4 Since then, the banana-phases exhibited by such compounds have been shown to possess a rich supermolecular stereochemistry, with examples of both macroscopic racemates and conglomerates represented. Indeed, the chiral banana phases formed from achiral or racemic compounds represent the first known bulk fluid conglomerates, identified 150 years after the discovery of their organic crystalline counterparts by Pasteur. A brief introduction to LCs as supermolecular self-assemblies, and in particular SmC ferroelectric and SmCA antiferroelectric LCs, followed by a snapshot of the rapidly evolving banana-phase stereochemistry story, is presented here. 

It is now instructive to ask why the achiral calamitic SmC a (or SmC) is not antiferroelectric. Cladis and Brand propose a possible ferroelectric state of such a phase in which the tails on both sides of the core tilt in the same direction, with the cores along the layer normal. Empirically this type of conformational ferroelectric minimum on the free-energy hypersurface does not exist in known calamitic LCs. Another type of ferroelectric structure deriving from the SmCA is indicated in Figure 8.13. Suppose the calamitic molecules in the phase were able to bend in the middle to a collective free-energy minimum structure with C2v symmetry. In this ferroelectric state the polar axis is in the plane of the page. 

Application of an electric field to the SmCsPA phase then causes the system to switch to a ferroelectric state. This could occur in two ways. The molecules in every other layer could simply rotate about the director, leaving the layer clinicity the same but changing the chirality of alternate layers. This would require a locally diastereomeric transition structure where the polarization is not parallel to the layers. 

Apparently this switching mode is disfavored since, in fact, the chirality of the layers does not change upon switching to the ferroelectric state rather the layer interface clinicity changes. This occurs when the molecules in alternate layers simply precess about the tilt cone in a manner exactly analogous to antiferroelectric to ferroelectric switching in the chiral SmC phase. As shown in Figure 8.25, the ferroelectric state obtained from the ShiCsPa antiferroelectric phase is a ShiCaPf structure, an achiral macroscopic racemate with anticlinic layer interfaces. 

Niori, T. Sekine, T. Watanabe, J. Furukawa, T. Takezoe, H. Distinct Ferroelectric Smectic Liquid Crystals Consisting of Achiral Molecules with Banana Shape, Abstracts of the 16th International Liquid Crystal Conference, Kent State University, Kent, OH, 1996, p. 126. 

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