Nematic potentials orientational distribution function

This can be inserted in equation (02.2.3) to give tlie orientational distribution function, and tlius into equation (02.2.6) to deteniiine the orientational order parameters. These are deteniiined self-consistently by variation of tlie interaction strength iin equation (c2.2.7). As pointed out by de Gemies and Frost [20] it is possible to obtain tlie Maier-Saupe potential from a simple variational, maximum entropy metliod based on tlie lowest-order anisotropic distribution function consistent witli a nematic phase. 

Figure I. Schematic representation of statistical orientational distribution functions in isotropic (I) and nematic (N) potentials. Dashed curves depict adjusted distributions under electric field poling.

From slow-shear-rate solutions of the Smoluchowski equation, Eq. (11-3), with the Onsager potential, Semenov (1987) and Kuzuu and Doi (1983, 1984) computed the theoretical Leslie-Ericksen viscosities. They predicted that ai/a2 < 0 (i.e., tumbling behavior) for all concentrations in the nematic state. The ratio jai is directly related to the tumbling parameter X by X = (1 -h a3/a2)/(l — aj/aa). Note the tumbling parameter X is not to be confused with the persistence length Xp.) Thus, X < I whenever ai/a2 < 0. As discussed in Section 10.2.4.1, an approximate solution of Eq. (11-3) predicts that for long, thin, stiff molecules, X is related to the second and fourth moments Sa and S4 of the molecular orientational distribution function (Stepanov 1983 Kroger and Sellers 1995 Archer and Larson 1995) ... 

We now use the Debye equation to treat molecular reorientation in a nematic liquid crystal [7.1, 7.2] by suitably modifying the equation to allow for an ordering potential that is known to be present in the mesophase. The orientational distribution function f Cl) and the conditional probability function f Qo n,t) are obtained by solving... 

Earlier, in Chapter 3, the existence of the nematic phase was presented as an example of an order-disorder phenomenon. The symmetry and structure of the nematic phase were used to identify the natural order parameter , where P2 (cos d) is the second Legendre polynomial and the angular brackets denote a statistical average over the orientational distribution function /(cos 6). The orientational potential energy of a single molecule was shown, in the mean field approximation, to be... 

One of the primary features of the Gay-Berne potential is the presence of anisotropic attractive forces which should allow the observation of thermally driven phase transitions and this has proved to be the case. Thus using the parametrisation proposed by Gay and Berne, Adams et al. [9] showed that GB(3.0, 5.0, 2, 1) exhibits both nematic and isotropic phases on varying the temperature at constant density. This was chosen to be close to the transitional density for hard ellipsoids with the same ellipticity indeed it is generally the case that to observe a nematic-isotropic transition for Gay-Berne mesogens the density should be set in this way. The long range orientational order of the phase was established from the non-zero values of the orientational correlation coefficient, G2(r), at large separations and the translational disorder was apparent from the radial distribution function. 

The nematic mean-field U, the molecule-field interaction potential, WE, and the induced dipole moment, ju d, are evaluated at different orientations using Equation (2.263), and then the coefficients of their expansion on a basis of Wigner rotation matrices can be calculated, according to Equation (2.268). The permittivity is obtained by a self-consistency procedure, because the energy WE and the induced dipole moment / md, as well as the reaction field contribution to the nematic distribution function p( l), themselves depend on the dielectric permittivity. 

The Maier-Saupe theory of nematic liquid crystals is founded on a mean field treatment of long-range contributions to the intermolecular potential and ignores the short-range forces [88, 89]. With the assumption of a cylindrically symmetrical distribution function for the description of orientation of the molecules and a nonpolar preferred axis of orientation, an appropriate order parameter for a system of cylindrically symmetrical molecules is... 

Fig. 2.3.5. Orientational distribution functiony(cos ) as defined by (2.3.22) in the nematic phase of MBBA. Circles represent values from Raman measurements and the line gives the distribution function derived from a two-term Maier-Saupe potential in which the parameters are adjusted to give a good fit with the observed

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. 

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