Liquid crystals molecular ordering

J. G., De Lange, G. A. Molecular solutes in nematic liquid crystals orientational order and electric field gradients. Chem. Phys. Lett. 1983, 99, 271-274. 

G. W. Gray, Molecular Structure and the Properties of Liquid Crystals , Academic Press, London, 1962 Liquid Crystals and Ordered Fluids , ed. J. F. Johnson and R. S. Porter, Plenum Press, New York, 1970. 

Under just the right conditions, a mixture of a highly polar liquid, a slightly polar liquid, and an amphiphilic molecule form micelles that are not spherical. They can be rodlike, disc-like, or biaxial (all three axes of the micelles are different). These anisotropic micelles sometimes order in the solvent just as liquid crystal molecules order in thermotropic phases. There is a nematic phase of rod-shaped micelles, another nematic phase of disc-shaped micelles, and even a biaxial nematic phase, in which the molecular axes transverse to the long molecular axis partially order. Chiral versions of these phases with the same structure as the chiral nematic phase also form. 

Figure 5.2. Monolayers of the amphiphile 1-monopalmitoyl-( )-glycerol at the air-water interface assemble in domains in which the molecular tilt azimuth is organized in star-shaped patterns. It is possible to preserve this order during the transfer on to a solid support. LB monolayers of this material have been utilized for the anchoring of nematic liquid crystals. The order within the monolayer determines the order within the bulk phase of the nematic liquid crystal (LC). The image here shows the LC cell between crossed polarizers. (From J. Fang, U. Gehlert, R. Shashidar and C. Knobler, Langmuir (1999), 15, 297)...

In order to use liquid crystalline polymers as commercial optical films, it is necessary to achieve both the immobilization of the liquid crystal molecular oriented structure and the orientation control of the liquid crystalline polymer. However, in the 1980s there was no technology that could satisfy both requirements and it was necessary to develop it ourselves. The key phrase at that time was do not be bound by common sense. ... 

The label liquid crystal seems to be a contradiction in tenns since a crystal cannot be liquid. However, tire tenn refers to a phase fonned between a crystal and a liquid, witli a degree of order intennediate between tire molecular disorder of a liquid and tire regular stmcture of a crystal. Wlrat we mean by order here needs to be defined carefully. The most important property of liquid crystal phases is tliat tire molecules have long-range orientational order. For tliis to be possible tire molecules must be anisotropic, whetlier tliis results from a rodlike or disclike shape. 

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. 

Kresge C T, Leonowicz M E, Roth W J, Vartuli J C and Beck J S 1992 Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism Nature 359 710-12... 

The liquid crystal polymers consist of rod-like molecules which, during shear, tend to orient in the direction of shear. Because of the molecular order the molecules flow past each other with comparative ease and the melts have a low viscosity. When the melt is cooled the molecules retain their orientation, giving self-reinforcing materials that are extremely strong in the direction of orientation. 

Liquid crystal polymers (LCP) are a recent arrival on the plastics materials scene. They have outstanding dimensional stability, high strength, stiffness, toughness and chemical resistance all combined with ease of processing. LCPs are based on thermoplastic aromatic polyesters and they have a highly ordered structure even in the molten state. When these materials are subjected to stress the molecular chains slide over one another but the ordered structure is retained. It is the retention of the highly crystalline structure which imparts the exceptional properties to LCPs. 

One type of material that has transformed electronic displays is neither a solid nor a liquid, but something intermediate between the two. Liquid crystals are substances that flow like viscous liquids, but their molecules lie in a moderately orderly array, like those in a crystal. They are examples of a mesophase, an intermediate state of matter with the fluidity of a liquid and some of the molecular order of a solid. Liquid crystalline materials are finding many applications in the electronics industry because they are responsive to changes in temperature and electric fields. 

Computer simulations therefore have several inter-related objectives. In the long term one would hope that molecular level simulations of structure and bonding in liquid crystal systems would become sufficiently predictive so as to remove the need for costly and time-consuming synthesis of many compounds in order to optimise certain properties. In this way, predictive simulations would become a routine tool in the design of new materials. Predictive, in this sense, refers to calculations without reference to experimental results. Such calculations are said to be from first principles or ab initio. As a step toward this goal, simulations of properties at the molecular level can be used to parametrise interaction potentials for use in the study of phase behaviour and condensed phase properties such as elastic constants, viscosities, molecular diffusion and reorientational motion with maximum specificity to real systems. Another role of ab initio computer simulation lies in its interaction... 

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]. 

At present there have been no attempts to explore the molecular electronic basis for liquid crystal anchoring or to calculate Rapini-Popoular coefficients for real systems using first principles methods. However, there have been a number of theoretical treatments which have suggested that the ordering of... 

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