Director helix, chiral nematics

Chira.lNema.tlc, If the molecules of a Hquid crystal are opticaHy active (chiral), then the nematic phase is not formed. Instead of the director being locaHy constant as is the case for nematics, the director rotates in heHcal fashion throughout the sample. This chiral nematic phase is shown in Figure 7, where it can be seen that within any plane perpendicular to the heHcal axis the order is nematic-like. In other words, as in a nematic there is only orientational order in chiral nematic Hquid crystals, and no positional order. Keep in mind, however, that there are no planes of any sort in a chiral nematic Hquid crystal, since the director rotates continuously about the heHcal axis. The pitch of the helix formed by the director, ie, the distance it takes for the... 

Figure 2.3 Schematic representation of the periodical helical structures of the chiral nematic (cholesteric) phase. The pitch of the helix corresponds to the rotation of the director through 360°. There is no layered structure in a chiral nematic. N. phase.

When the molecules that form a liquid-crystalline phase are chiral, the structure of these mesophases can have an additional property. In the chiral nematic phase (N ) the director precesses about an axis perpendicular to the director and describes in this way a helix (Figure 2.7). The pitch of a chiral nematic phase is the distance along the helix over which the director rotates over 360°. The chiral nematic phase is sometimes... 

When the nematic phase is composed of optically active materials (either a single component or a multicomponent mixture made up of chiral compounds or chiral compounds mixed with achiral materials), the phase itself becomes chiral and has reduced environmental space symmetry. The structure of the chiral nematic (or cholesteric) modification is one where the local molecular ordering is identical to that of the nematic phase, but in the direction normal to the director the molecules pack to form a helical macrostructure, see Fig. 5. As in the nematic phase the molecules have no long-range positional order, and no layering exists. The pitch of the helix can vary from about 0.1 x 10 m to almost infinity, and is dependent on optical purity and the degree of molecular... 

Fig. 1. Schematic representation of (a) nematic, (b) smectic and (c) cholesteric (or chiral nematic) liquid crystalline phases. In the nematic phase only orientational correlations are present with a mean alignment in the direction of the director n. In the smectic phase there are additional layer-like correlations between the molecules in planes perpendicular to the director. The planes, drawn as broken lines, are in reality due to density variations in the direction of the director. The interplane separation then corresponds to the period of these density waves. In the cholesteric phase the molecules lie in planes (defined by broken lines) twisted with respect to each other. Since the molecules in one plane exhibit nematic-like order with a mean alignment defined by the director n, the director traces out a right- or left-handed helix on translation through the cholesteric medium in a direction perpendicular to the planes. When the period of this helix is of the order of the wavelength of light, the cholesteric phase exhibits bright Bragg-like reflections. In these illustrations the space between the molecules (drawn as ellipsoids for simplicity) will be filled with the alkyl chains, etc., to give a fairly high packing...

The cholesteric or chiral nematic phase may be considered as a perturbed planar nematic phase in which the director in each plane is slightly rotated with respect to that of an adjacent plane. Asymmetry in the chemical structure causes this rotation which results in the director tracing out a left- or right-handed helix. When such helix pitch... 

The director configuration of a chiral nematic hquid crystal is a good example of how the free ener expression ean be used. The eomponents of the director of the chiral nematic in Figure 1.11 assuming (1) the vertical direction is the z-axis, (2) the horizontal direction is the x-axis, and (3) the helix is right-handed are... 

The chiral nematic phase has a structure that is similar to the conventional, achiral nematic phase except that the reduced symmetry of the phase causes the molecular director to be gradually rotated at a shght angle through a section of the phase structure to describe a helix (see Chapter 6). 

The chiral nematic phase is characterized by a helical structure, and so the electric permittivity is biaxial, with three independent components along the principal axes, which are the local director axis, the helix and a third orthogonal axis. Since the pitches of chiral nematics are usually many molecular diameters, chiral nematics are locally uniaxial, and the pitch does not affect the symmetry or the magnitude of the permittivity. 

The lowest energy state for this structure is where the director describes a helix along one of the axes. Thus assuming that there is no bend or splay strain energy, a chiral nematic has a director configuration such that ... 

External field distortions in SmC and chiral SmC phases have been investigated [38], but the large number of elastic terms in the free-energy, and the coupling between the permanent polarization and electric fields for chiral phases considerably complicates the description. In the chiral smectic C phase a simple helix unwinding Fr6ede-ricksz transition can be detected for the c director. This is similar to the chiral nematic-nematic transition described by Eq. (83), and the result is identical for the SmC phase. Indeed it appears that at least in interactions with magnetic fields in the plane of the layers, SmC and SmC phases behave as two dimensional nematics [39]. 

In contrast to nematics, a helical twist of the molecular director takes place in the chiral nematic phase. Studies of the spin-lattice relaxation in chiral nematics have shown that the relaxation mechanisms are essentially the same as in pure nematics [141, 142]. At high Larmor frequencies the relaxation is diminished by molecular self-diffusion and by local molecular rotations, whereas director fluctuations determine the relaxation rate at low Larmor frequencies. This can be easily understood because the spin-lattice relaxation rate in the MHz region is dominated by orientational fluctuations with wavelength much smaller than the period of the helix. The influence upon the rotating frame spin-lattice relaxation time Tip of the rotation of the molecules due to diffusion along the helix, an effect specific for twisted structures, has not been observed in COC [143]. 

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