Molecular polarisability anisotropy

Molecular polarisability anisotropy and high order multipoles... 

The dielectric constants of an aligned nematic phase are dependent upon both the temperature and the frequency of the applied field at temperatures below the clearing point. The dielectric permitivity, j, measured parallel to all three axes above the clearing point in the isotropic liquid is the same. Therefore, the dielectric anisotropy of the same compound in the liquid state is zero, see Figure 2.10. The sign and magnitude of the dielectric constants and, therefore, the dielectric anisotropy are dependent upon the anisotropy of the induced molecular polarisability, Aa, as well as the anisotropy and direction of the resultant permanent molecular polarisation determined by permanent dipole moments. 

As discussed in Section 4.1, the specific adsorption of the ionic porphyrins at the liquid/liquid interface manifests itself by changes in the distribution of ions at the interface as well as in the interfacial tension. However, these two parameters do not provide direct information on the organisation of the adsorbed species in terms of lateral interactions and average molecular orientation. These aspects will be reviewed in Section 4.2 based on SHG and photocurrent Ught polarisation anisotropy studies of metalloporphyrins at the polarised water/IX2E interface. 

EQNS (1), (2) and (3) are commonly used as the basis of the molecular interpretation of the static permittivities measured as a function of temperature (e.g. [6,12-15,20,21,28-30,36,37]) and/or pressure [30,38]. Recently, quite successful predictions of anisotropic optical and dielectric constants from molecular modelling calculations were achieved with the aid of the Maier-Meier theory [39,40]. It seems worthwhile, therefore, to analyse these equations in order to point out the weak and strong points of the theory. EQN (3) is the most convenient for this purpose (both components of the permittivity are discussed by Jadzyn et al in a recent paper [41]). The parameters N, F and h in the Maier-Meier equations vary little with temperature. Therefore, the contribution from the polarisability anisotropy Aa to A8 varies with temperature in the same way as the order parameter S, whereas that connected with the orientation polarisation varies like S/T. Especially interesting seems to be the case of constant temperature discussed in [38] where As was measured as a function of pressure, p. The discussion of the measured permittivities, Sj and the anisotropy As as a function of the order parameter S obtained from the independent experiment seems to be the best way of verifying the assumptions on which the theory is based. 

Apart from high strength materials formed from nematic polymer fibres, most applications of nematic liquid crystals depend on their anisotropic optical properties. As a consequence the refractive indices of nematics are of prime importance in the development of materials for applications. The refractive indices are determined by the molecular polarisability coupled to the mientational order of the mesogens in the liquid crystal phase, so refractive indices can provide a direct probe of the order parameter. Furthermore the optical properties of liquid crystal films are frequently used to determine phase behaviour, identify phase types through characteristic optical textures or explore the properties of defects, and such experiments rely on the anisotropy in the refractive index of the material. The first tool of a liquid crystal scientist is the polarising microscope, which emphasises the importance of optical properties in general and refractive indices in particular to the stufy of liquid crystals. 

The optical anisotropy (i.e. the birefringence) of a nematic liquid crystal is a very important property for the contrast ratio and viewing angle in liquid crystal displays. The optical anisotropy of the nematic is caused by the anisotropy of the molecular polarisability of the constituent anisometric molecules (rod-like molecules) and their long range orientational ord. ... 

Anisotropy in polymer solutions is rather rare, but, where it occurs, the effect on the derived molecular weight can be large enough to warrant appropriate corrections. The procedures have been developed by Utiyama124) and by Utiyama and Kurata125). Without a polariser or analyser the normal reciprocal scattering function Kc/Rtf can be measured. It is denoted by Z(0) the form of which contains an anisotropy parameter 5 which is a function of the number of optically anisotropic elements and the principal polarisabilities in the chain ... 

While the orientation of these deuterated chains shows a strong molecular weight dependence especially at short times, all chains exhibit a relatively constant residual orientation at long times. Even chains of molecular weight as low as 3000 present a non-zero local orientation. This was confirmed by polarisation modulation infrared dichroism - a technique sensitive to very small anisotropies [34]. 

Steady-state fluorescence anisotropy In low-viscosity solvents the rotational depolarization of low molecular weight compounds occurs on the picosecond timescale [124]. Since in this case the rotation is much faster than the fluorescence, the steady-state emission is unpolarised. If the rotational motion of the fluorophore is on the same timescale as the fluorescence, a steady state polarisation is observed. In the simplest case for a spherical rotor and a single-exponential fluorescence intensity decay (r), the measured anisotropy is given by... 

Consequently, the Raman scattered light emanating from even a random sample is polarised to a greater or lesser extent. For randomly oriented systems, the polarisation properties are determined by the two tensor invariants of the polarisation tensor, i.e., the trace and the anisotropy. The depolarisation ratio is always less than or equal to 3/4. For a specific scattering geometry, this polarisation is dependent upon the symmetry of the molecular vibration giving rise to the line. 

Molecular Orientation Studied by Polarisation Angle Photocurrent Anisotropy... 

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