Nematic liquid crystal phase stability

The stability of the nematic liquid-crystal phase arises from the existence of strong interactions between pairs of the constituent molecules. As in normal liquids, the potential of interactions will have attractive contributions to provide the cohesion of the fluid, and repulsive contributions which prevent the interpenetration of the molecules. In the case of the rod-like molecules of nematics, however, these interactions are highly anisotropic. That is, the forces acting between such molecules depend not only on their separation but also, and most importantly, on their mutual orientations. From the symmetry and structure of the nematic phase, we see that the rod-like molecules in fact interact in a manner that favors the parallel alignment of neighboring molecules. 

The use of latoal substituents in liquid crystals has proved to be very important, initially in nematic material and lata- in smectic C matoials. Clearly, anything that sticks off the side of a rod-like molecule will tend to reduce the liquid crystal phase stability, and genmlly the larg the lateral substituent the greater the reduction in liquid crystal phase stability. Usually, the smectic phase stability is much mmre affected than that of the nematic phas especially by larger substitumts because of the obvious reduction in lateral attractions, but increased lateral attractions associated with polar substituents cause a smaller reduction in smectic phase stability (see compounds 52-57) [46]. 

Mixtures of a nematic liquid crystal (LC or LC ) with small quantities of gold nanoparticles coated with alkylthiolates (<5 wt%) including an alkylthiolate functionalized with a chiral group have been studied (Figure 8.29) [72]. All mixtures show nematic mesophases with transition temperatures and phase stability very similar to those oftheliquid crystal precursors LC or LC. The introduction ofachiral center into the mixtures (mixtures of Au ) produce chiral nematic mesophases. A similar result is obtained in mixtures of Au and LC doped with the chiral dopant (s)-Naproxen. 

The nematic phase (N) is the least ordered, and hence the most fluid liquid crystal phase. The order in this type of LC phases is based on a rigid and anisometric (in most cases rod-shaped or disc-shaped) molecular architecture. Such molecules tend to minimize the excluded volume between them, and this leads to long range orientational order. For rod-like molecules the ratio between molecular length and its broadness determines the stability of the nematic phase with respect to the isotropic liquid state and the stability rises with increase of this ratio. In most cases the rigid cores are combined with flexible chains, typically alkyl chains, which hinder crystallization and in this way retain fluidity despite of the onset of order. 

Depending on temperature, transitions between distinct types of LC phases can occur.3 All transitions between various liquid crystal phases with 0D, ID, or 2D periodicity (nematic, smectic, and columnar phases) and between these liquid crystal phases and the isotropic liquid state are reversible with nearly no hysteresis. However, due to the kinetic nature of crystallization, strong hysteresis can occur for the transition to solid crystalline phases (overcooling), which allows liquid crystal phases to be observed below the melting point, and these phases are termed monotropic (monotropic phases are shown in parenthesis). Some overcooling could also be found for mesophases with 3D order, namely cubic phases. The order-disorder transition from the liquid crystalline phases to the isotropic liquid state (assigned as clearing temperature) is used as a measure of the stability of the LC phase considered.4... 

Lopatina and Selinger recently presented a theory for the statistical mechanics of ferroelectric nanoparticles in liquid crystals, which explicitly shows that the presence of such nanoparticles not only increases the sensitivity to applied electric fields in the isotropic liquid phase (maybe also a possible explanation for lower values for in the nematic phase) but also 7 N/Iso [327]. Another computational study also supported many of the experimentally observed effects. Using molecular dynamics simulations, Pereira et al. concluded that interactions between permanent dipoles of the ferroelectric nanoparticles and liquid crystals are not sufficient to produce the experimentally found shift in 7 N/ so and that additional long-range interactions between field-induced dipoles of nematic liquid crystal molecules are required for such stabilization of the nematic phase [328]. 

The synthesis of a great number of materials that exhibit the nematic phase has achieved many different goals. Firstly, much knowledge has been acquired of the effect of stmctural features and various combinations of stmctiual features on melting points, mesophase morphology, and stability. Secondly, many physical properties have been evaluated for a great niunber of nematic liquid crystals and the resrrlts have been linked to the stmcture. Thirdly, mixtures of nematic materials have been formulated that have been... 

One of the intrinsic problems for the practical application of FLC displays is the low mechanical stability of the molecular orientations. The initial molecular orientations in an FLC material are easily destroyed by the application of mechanical pressure and/or mechanical shock. The materials do not return to their initial states, unlike molecular orientations in nematic liquid crystals, which are also disturbed by mechanical pressure and/or shock but usually return to their initial states. The low stability of FLC devices under exposure to shock is attributed to the presence of the smectic layer structure. The molecular orientation of the smectic phases is highly ordered in comparison with that of the nematic phase. 

However, the number of liquid crystals that have been studied under pressure is very limited. In most cases neither the equation of state nor the pressure dependence of the order parameter is known. Only the mean-field theory of Maier and Saupe was extended to explain the dielectric properties of liquid crystalline phases. However, a recent approach by Photinos et al. analyzed the nematic reentrance and phase stability based on the variational cluster method. The lack of a full theoretical description as well as insufficient experimental data should stimulate further high-pressure investigations in this field. 

An important aspect of the macroscopic structure of liquid crystals is their mechanical stability, which is described in terms of elastic properties. In the absence of flow, ordinary liquids cannot support a shear stress, while solids will support compressional, shear and torsional stresses. As might be expected the elastic properties of liquid crystals are intermediate between those of liquids and solids, and depend on the symmetry and phase type. Thus smectic phases with translational order in one direction will have elastic properties similar to those of a solid along that direction, and as the translational order of mesophases increases, so their mechanical properties become more solid-like. The development of the so-called continuum theory for nematic liquid crystals is recorded in a number of publications by Oseen [ 1 ], Frank [2], de Gennes and Frost [3] and Vertogen and de Jeu [4] extensions of the theory to smectic [5] and columnar phases [6] have also been developed. In this section it is intended to give an introduction to elasticity that we hope will make more detailed accounts accessible the importance of elastic properties in determining the... 

This group has a characteristically flat disk shape, which is responsible for the discotic liquid crystal phase. The nickel bis (dithiolene) core has high thermal and photochemical stability. The substituted R groups impart the solubility in nonpolar solvents. Also, if the R groups are sufficiently long, they can form a nematic liquid crystal, as shown in Figure 5 and 6. 

More recently, direactive liquid crystals have been added to an aligned liquid crystal phase and the film photopolymerized in the liquid crystal phase. A range of displays (called polymer-stabilized displays) have been demonstrated, the most notable using a chiral nematic host with a pitch either in the visible (to produce green and black displays) or in the infrared (to produce scattering to clear states). In each case the devices are bistable, thus allowing complex displays to be made. 

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