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Nematic-Isotropic Transition Molecular Approach

The degree of orientational order in a uniaxial nematic is given by the order parameter S, defined by Eq. (2-3). S is zero in the isotropic state, and it approaches unity for hypothetically perfect molecular alignment (i.e., all molecules pointing in the same direction). In single-component small-molecule nematics, such as MBBA, S varies with temperature from 5 0.3 at Tni, the nematic-isotropic transition temperature, to S 0.7 or so at lower... [Pg.447]

Analytical approaches to understanding the effect of molecular flexibility on orientational order have concentrated on both the isotropic-nematic and the nematic-smectic transition [61, 62] and mean field theory has shown that cholesteric pitch appears not to depend on the flexibility of the molecule [63]. [Pg.27]

The third problem is the possible effect of stress or external field on isotropic-nematic phase transition. In equilibrium, this phase transition is usually described by the well-known Landau phenomenology or more specifically (however, less reliably because of large fluctuations) by the Maier-Saupe mean field theory [2] (see also Refs [30,31 ]). The assumption that the transition behavior of nematic elastomers is independent of stress was roughly confirmed while testing the LCE theory [3], where the parameters of anisotropy were assumed to be independent of stress. The possible dependences of scalar/tensor order parameter on stress/extemal field have been considered in molecular Doi theory [9, 11] or phenomenological approach by Ericksen [41]. [Pg.502]

A similar approach has been used to produce materials with a chiral (cholesteric) structure by performing the experiments described above in the presence of a low molecular weight chiral liquid crystalline material (Figure 9.6). The chiral material is not covalently attached to the network and can be removed subsequently to produce an imprinted chiral structure. As before, the polymer displays a nematic mesophase between the glass transition (Tg 33°C) and the transition to an isotropic fluid (rN, 128°C). [Pg.237]

Liquid crystals manifest a number of transitions between different phases uprm variation of temperature, pressure or a craitent of various compounds in a mixture. All the transitions are divided into two groups, namely, first and second order transitions both accompanied by interesting pre-transitional phenomena and usually described by the Landau (phenomenological) theory or molecular-statistical approach. In this chapter we are going to consider the most important phase transitions between isotropic, nematic, smectic A and C phases. The phase transitions in ferroelectric liquid crystals are discussed in Chapter 13. [Pg.111]

The nematic phase being the liquid crystal of highest symmetry, its condensation from the isotropic liquid should be the simplest to describe. Indeed, molecular theories convincingly explain the natural onset of nematic ordering in a population of anisotropic molecules with excluded volume interaction (Onsager) or in mean field theory (Maier-Saupe). Regarding the effect of symmetry on the isotropic to nematic (I-N) phase transition, the phenomenological approach is useful too. [Pg.314]

In this chapter we consider the very simplest approach to the molecular theory of liquid crystals. We shall approach the theory phenomenologically, treating the problem of the existence of the nematic phase as an order-disorder phenomenon. Using the observed symmetry of the nematic phase we shall identify an order parameter and then attempt to find an expression for the orientational potential energy of a molecule in the nematic liquid in terms of this order parameter. Such an expression is easily found in the mean field approximation. Once this is accomplished, expressions for the orientational molecular distribution function are derived and the thermodynamic functions simply calculated. The character of the transformation from nematic liquid crystal to isotropic fluid is then revealed by the theory, and the nature of the fluctuations near the transition temperature can be explored. [Pg.31]

To avoid phase separation between the two moieties, a vast effort was devoted towards the synthesis of chemically linked disc-rod molecules [25-27], Beyond that, mixtures of prolate and oblate mesogens have stimulated theorists to perform intensive computer simulations. Simulations and molecular field theories predict the biaxial nematic phase to occur around the minimum of the transition temperature T from the nematic to the isotropic phase [22]. Furthermore, a strong decrease of the transition enthalpy is expected upon approaching the tricritical point. [Pg.108]

The values of the scaled transition temperature, l TNi/e2oo, together with the transitional values of the ord parameters ni, ni and ni are listed in TABLE 1 for several values of the biaxiality parameter, X. As the molecular biaxiality increases so the major order parameter at the transition decreases indeed when X is 0.3 ni has decreased to about half that for a uniaxial molecule. In contrast although as expected the biaxial ordo- parameter ni increases with X the value is extremely small. It would seem, therefore, that the molecular biaxiality has the greatest effect on Ni and that ni is essentially negligible. The influence of X on the second rank order parameter is mimicked by its fourth rank counterpart ni indeed when X is 0.3 this order parameter is four times smaller than that for uniaxial molecules. For X of 0.4 all of the transitional order parameters are extremely small, hinting at the approach of a second ord transition. This occurs when X is 1 / >/6 but now the transition from the isotropic phase is directly to a biaxial and not a uniaxial nematic phase, as we shall see. [Pg.92]

MD-EPR approach has also been sueeessfully applied to study the dy-namies and ordering of the molecules in the bulk phases of soft matter systems sueh as nematic liquid crystals nCB doped with nitroxide spin probes. MD simulations have been reported at both coarsegrained and fully atomistic levels. Predicted ehanges in molecular order, dynamics and variable temperature EPR line shapes across the nematic (N) to isotropic (I) phase transitions showed excellent agreement with experiment. A combined MD-EPR approach provides a new level of detail to descriptions of molecular motions and order. Figure 7 shows snapshots of isotropie (top) and nematic (bottom) states of 8CB with doped CLS spin probe. It also presents comparison between predicted and measured EPR spectra of 8CB along the N-I phase transition curve... [Pg.51]


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Molecular approach

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