Relative optical anisotropy

Fig. 1. Degree of orientational order S (Curve 1) and relative optical anisotropy (Y1-Y2)/Yi"Y2) x-> > (curve 2) vs. parameter x=2L/A.

Film preparation plays a crucial role in determining the photoelectrochemical properties of phthalocyanine electrodes. Since the coupling of individual chromophores strongly depends on their relative orientation, the position of the absorption maximum and its width shows a clear dependence on the structure of thin films. Also the charge transport within phthalocyanine films, a fundamental necessity for the films to work as electrodes, depends upon the overlap of the frontier orbital wave functions. Beyond the microscopic structure of films also the morphology of films plays an important role. In the case of crystalline films, the orientation of crystallites relative to the electrode surface will be relevant because of anisotropies in optical absorption and charge transport. The size of the observed photocurrent directly depends on the real electrode surface area accessible by the electrolyte and this leads to a strong dependence on the porosity of the films. 

Another important linear parameter is the excitation anisotropy function, which is used to determine the spectral positions of the optical transitions and the relative orientation of the transition dipole moments. These measurements can be provided in most commercially available spectrofluorometers and require the use of viscous solvents and low concentrations (cM 1 pM) to avoid depolarization of the fluorescence due to molecular reorientations and reabsorption. The anisotropy value for a given excitation wavelength 1 can be calculated as... 

Today generator matrices F are known for many properties,10 among them the population of different conformers, the relative stability of macromolecular diastereoisomers, the mean-square end-to-end distance, the radius of gyration, the molecular dipole moment, the molecular optical anisotropy (and, with it, the stress-optical coefficient, the Kerr effect, depolarized light scattering, and the... 

The stress-optical coefficient of PE networks is calculated, and results are compared with experimental data. Observed temperature coefficients of AT and the optical anisotropy for unswollen samples are much larger than those calculated using acceptable values of E(g), the energy of the gauche conformation, relative to that of Vans. It is concluded that observed temperature coefficients should Include some contributions other than those implied in the theory, i.e., those arising from the conformational change with temperature. 

Chromophores which are asymmetric by nature are characterized by the absence of a center and plane of symmetry in the group of atoms participating in the optical transition. The rotational strength of these are usually larger when compared with chromophores that become optically active due to substitution. This is demonstrated in Mason and Schnepp s8 study of trans-cyclooctene, a-pinene and /1-pi none. They pointed out that the g (anisotropy factor, g = Ae/e) value of the major bands in trans -cyclooctene is relatively high as expected for an intrinsically asymmetric chromophore when compared with the other two olefins. 

In order to examine the optical anisotropy, we begin with the relative permittivity tensor for the system , which is defined (see, for example, Born and Wolf 1970 Landau et al. 1987) by the relation... 

In the simplest cases, the optical anisotropy of polymer systems is studied under the conditions of simple elongation, when the elongation velocity gradient i/ii is given. The system investigated then becomes, generally speaking, a triaxial dielectric crystal with components of the relative permittivity tensor... 

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