Structural liquid crystal phases

Pershan P S 1988 Structure of Liquid Crystal Phases (Singapore World Soientifio)... 

It follows from general considerations that the role of the shape of the filler particles during net-formation must be very significant. Thus, it is well-known that the transition from spherical particles to rod-like ones in homogeneous systems results in such radical structural effect as the formation of liquid-crystal phase. Something like that must be observed in disperse systems. 

This article reviews progress in the field of atomistic simulation of liquid crystal systems. The first part of the article provides an introduction to molecular force fields and the main simulation methods commonly used for liquid crystal systems molecular mechanics, Monte Carlo and molecular dynamics. The usefulness of these three techniques is highlighted and some of the problems associated with the use of these methods for modelling liquid crystals are discussed. The main section of the article reviews some of the recent science that has arisen out of the use of these modelling techniques. The importance of the nematic mean field and its influence on molecular structure is discussed. The preferred ordering of liquid crystal molecules at surfaces is examined, along with the results from simulation studies of bilayers and bulk liquid crystal phases. The article also discusses some of the limitations of current work and points to likely developments over the next few years. 

Molecular Structure in Thermotropic Liquid Crystal Phases. 58... 

Molecular mechanics force fields have largely been parameterised using the best available data from the gas phase and (in some cases) from liquid phase or solution data. The question therefore arises as to how applicable molecular mechanics force fields are to predicting structures of molecules in the liquid crystal phase. There is now good evidence from NMR measurements that the structure of liquid crystal molecules change depending on the nature of their... 

The anisotropy of the liquid crystal phases also means that the orientational distribution function for the intermolecular vector is of value in characterising the structure of the phase [22]. The distribution is clearly a function of both the angle, made by the intermolecular vector with the director and the separation, r, between the two molecules [23]. However, a simpler way in which to investigate the distribution of the intermolecular vector is via the distance dependent order parameters Pl+(J") defined as the averages of the even Legendre polynomials, PL(cosj r)- As with the molecular orientational order parameters those of low rank namely Pj(r) and P (r), prove to be the most useful for investigating the phase structure [22]. 

It is now well-established that for atomic fluids, far from the critical point, the atomic organisation is dictated by the repulsive forces while the longer range attractive forces serve to maintain the high density [34]. The investigation of systems of hard spheres can therefore be used as simple models for atomic systems they also serve as a basis for a thermodynamic perturbation analysis to introduce the attractive forces in a van der Waals-like approach [35]. In consequence it is to be expected that the anisotropic repulsive forces would be responsible for the structure of liquid crystal phases and numerous simulation studies of hard objects have been undertaken to explore this possibility [36]. 

In most cases the order of elution for a series of isomers on liquid crystalline stationary phases is generally in accord with the solute length-to-breadth ratios with differences in vapor pressure and solute polarity also being of Importance in some cases, leading to an inversion of elution order to that predicted from length-to-breadth ratios [828,829,838]. Long and planar molecules fit better into the ordered structure of the liquid crystal phase whereas nonlinear and nonplanar molecules do not permeate so easily between the liquid crystal molecules of the stationary phase and are more easily eluted from the column. 

When a molecule exhibits large internal motions difficulties arise in using most available techniques for the determination of molecular geometry. In a study of 2,2 -biselenophene it was shown that although internal motion is present, useful structural information can still be obtained in the liquid crystal phase and that, at present, other techniques are not available for obtaining equivalent information, at least not in a liquid-like phase.13 This study also demonstrates the usefulness of the heteroatom satellites, and in particular of Se—H dipolar couplings. 

Figure 8.17 Structure and phase sequence of first banana-phase mesogen, reported by Vorlander in 1929, is given. Liquid crystal phase exhibited by this material (actually Vorlander s original sample) was shown by Pelzl et al.36a to have B6 stmeture, illustrated on right, in 2001. Achiral B6 phase does not switch in response to applied fields in way that can be said to be either ferroelectric or antiferroelectric.

Since Robinson [1] discovered cholesteric liquid-crystal phases in concentrated a-helical polypeptide solutions, lyotropic liquid crystallinity has been reported for such polymers as aromatic polyamides, heterocyclic polymers, DNA, cellulose and its derivatives, and some helical polysaccharides. These polymers have a structural feature in common, which is elongated (or asymmetric) shape or chain stiffness characterized by a relatively large persistence length. The minimum persistence length required for lyotropic liquid crystallinity is several nanometers1. 

These materials had helical structures of rigid-rod shapes and exhibited a liquid-crystal phase either in an organic solvent or in the molten state. 

The crystallinity of liquid crystal phases refers to the large assortment of ways these micellar structures can be organized within a bulk phase. For example, spherical micelles of... 

FIG. 8.8 Schematic representations of surfactant structures in (a) viscous isotropic, (b) middle, and (c) neat liquid crystal phases. 

Liquid Crystals Liquid-crystal phases may occur between the solid and the liquid phase. Cholesteryl myristate, for example, exists in a liquid-crystal phase between 71 and 85°C [6]. The appearance of liquid-crystal phases depends on the molecular structure. Compounds with elongated structures that are fairly rigid in the central part of the molecule are likely candidates for liquid crystals. The homologous series of p-alkoxybenzylidene-p-n-butylanilines is just one example for compounds with liquid-crystal phases. An excellent introduction to liquid crystals and their properties has been written by Collings [6]. 

Just because a molecule is long, narrow, and meets the requirement of geometric anisotropy docs not ensure that it will have a liquid crystal phase. The particular phase structure that occurs in a compound, i.e.. smectic, nematic, or chiral nematic, not only dc >cnds on the molecular shape hut is intimately connected with the strength and position of the polar or polarizable groups within the molecule, the overall polarizability of the molecule, and the presence ol chiral centers. 

Phase structure Equivalent smectic liquid crystal phase... 

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