Translational orientational correlations

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. 

Given the character of the water-water interaction, particularly its strength, directionality and saturability, it is tempting to formulate a lattice model, or a cell model, of the liquid. In such models, local structure is the most important of the factors determining equilibrium properties. This structure appears when the molecular motion is defined relative to the vertices of a virtual lattice that spans the volume occupied by the liquid. In general, the translational motion of a molecule is either suppressed completely (static lattice model), or confined to the interior of a small region defined by repulsive interactions with surrounding molecules (cell model). Clearly, the nature of these models is such that they describe best those properties which are structure determined, and describe poorly those properties which, in some sense, depend on the breakdown of positional and orientational correlations between molecules. 

The mean diffusional structure (structure D) is that obtained with an exposure time of the order of the orientational correlation time (or of the translational counterpart) of the molecule. This structure has also been explored by computer simulation experiments,but the agreement between the results and experiment is not always satisfactory. 

Translational-orientational fluctuations. Re-writing the expansion (195) of the optical polarizability deviation tensor in a manner adapted to multi-component systems (as done previously for electric polarizability), one obtains from the general formula an additional contribution from binary correlations of axially symmetric molecules, of the form ... 

Analogous to equation (8) the vibrational densities of states D " u) are calculated for the cases of CO and CS2 at two different pressures, respectively. They are shown in Figure 4 while Table 4 contains information about their positions and widths. Since under the similarity transformation the trace of V is preserved and because the relative band widths are small, the spectra are centred around the natural oscillator frequency uiq. The widths of the distributions depend on the strength of coupling between two oscillators which, apart from factors of positional and orientational correlation, scale linearly with transition dipole (dfijd(,Y and density p (equation (14)). CO is regarded as a reference system because of its simple translational and minor orientational structure. The last column in Table 4 expresses the influence of liquid structure on band width. All densities of states... 

ISS data have been recorded in many pure and mixed molecular liquids [34,49, 75, 83, 83-85], In most cases, the data are not described precisely by Eq. (27). Rather, an additional decay component appears at intermediate times (decay times 500 fs). This has been interpreted [49, 84] in terms of higher order polarizability contributions to C (t) which represent translational motions, an interpretation supported by observations in CCI4 (whose single-molecule polarizability anisotropy vanishes by symmetry). This interpretation is not consistent with several molecular dynamics simulations of CSj [71, 86]. An alternative analysis has been presented [82] that incorporates theoretical results showing that even the single-molecule orientational correlation function C (t) should in fact show decay on the 0.5-ps time scale of cage fluctuations [87, 88]. 

The local sixfold bond orientational order parameter is defined in Eq. (3.3). g FpFj) is divided out of Eq. (3.15) in order to remove translational correlations from the bond orientational correlation function. In the homogeneous and isotropic liquid phase gl (r,F2) reduces to a function of Fj, only, which we will denote by g r), and a corresponding translation- and rotation-invariant quantity can be defined for the solid phase by performing suitable averages. 

The true smectic phases are more highly ordered than the nematic phase and are characterized by partial translational ordering of the molecules into layers, in addition to orientational correlations. The simplest smectic phase is the smectic A (SmA) phase which is represented schematically in Figure 7(a). As in the nematic phase, the... 

In addition, protein motion reduces the retardation of the water dynamics, because the dimension of the water translational space is increased and at the same time the decay of the orientational correlation is accelerated. In spite of this accelerated dynamics, hydration water diffusion remains anomalous for a thermalized protein. 

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...

FIGURE 2.6 (Upper panel) Plot for the reorientational correlation function against time for a representative composition (Xj = 0.1). (Lower panel) Product of the translational diffusion coefficient Dj. and the average orientational correlation time x, of the first-rank correlation function as a function of composition. Note that the solid line and dashed line indicate the hydrodynamic predictions with the stick and slip boundary conditions, respectively. 

There has been much activity in the study of monolayer phases via the new optical, microscopic, and diffraction techniques described in the previous section. These experimental methods have elucidated the unit cell structure, bond orientational order and tilt in monolayer phases. Many of the condensed phases have been classified as mesophases having long-range correlational order and short-range translational order. A useful analogy between monolayer mesophases and die smectic mesophases in bulk liquid crystals aids in their characterization (see [182]). 

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