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spectroscopy, the three orthogonal refractive indices in an oriented sample can be measured (Tawa and Knoll, 2002) Stokes polarimetry can be used to fully characterize the optical anisotropy, separating linear and circular components (Hore et al, 2002) The anisotropy of the cis population during irradiation can also be measured in some systems (Buffeteau et al, 2001; Sekkat et al, 1995b), where it is found that, as with trans, there is an enrichment perpendicular to the irradiation polarization In some LC systems, however, it may occur that the cis population preferentially aligns with the irradiating polarization (which may be attributed to an optical Freedericksz transition) (Hore et al, 2003) The birefringence can be written and erased hundreds of thousands of times, which is important technologically (Holme et al, 1996) Amorphous polymer systems with relatively high Tg exhibit good temporal stability of any induced orientation.

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materials (electrolytes, electrodes, non-aqueous electrochemistry in general), up-to-date charge transfer theory and biological aspects of electrochemistry. On the other hand, the presentation of electrochemical methods is quite short as the reader has access to excellent monographs on the subject (see page 301). The Czech manuscript has been kindly translated by Dr M. HymanStulikova. We are much indebted to the late Dr A Ryvolova, Mrs M. Kozlova and Mrs D. Tumova for their expert help in preparing the manuscript. Professor E. Budevski, Dr J. Ludvik, Dr L. Novotny and Dr J. Weber have supplied excellent photographs and drawings. Dr K. Janacek, Dr L. Kavan, Dr K. Micka, Dr P. Novak, Dr Z. Samec and Dr J. Weber read individual chapters of the manuscript and made valuable comments and suggestions for improving the book. Dr L. Kavan is the author of the section on non-electrochemical methods (pages 319 to 329). We are also grateful to Professor V. Pokorny, Vice-president of the Czechoslovak Academy of Sciences and chairman of the Editorial Council of the Academy, for his support. Lastly we would like to mention with devotion our teachers, the late Professor J. Heyrovsky and the late Professor R. Brdicka, for the inspiration we received from them for our research and teaching of electrochemistry, and our colleague and friend, the late Dr V. Bohackova, for all her assistance in the past. Prague, March 1986 Jifi Koryta Jin Dvorak

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178 178

i,f-(^f- )

Upon heating, some order will be lost, with full isotropy restored after heating past Tg A short spacer between the chromophore and the polymer backbone slows the growth of birefringence yet promotes stability, owing to hindered motion Surprisingly, main-chain azos can achieve high levels of birefringence, indicating relatively high polymer mobility (Wu et al, 2001b; Xu et al, 2000; Lee et al, 1998) As might be expected, (nanosecond) pulsed experiments lead to thermal effects, which enhance chromophore motion and thereby induced greater birefringence at the same net dose compared with continuous-wave (cw) experiments (Cimrova et al, 2002; Hildebrandt et al, 1998) At very high pulsed uence, the thermal effects were too great and erased the induced birefringence The easily inscribed and erased birefringence has a number of unique applications Most readily, it can be used to create wave plates (Shi et al.

(1.3.2)

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, 1991a) and polarization lters, which can be used to separate right-handed from left-handed circularly polarized light (Natansohn and Rochon, 1999) The strong refractive index contrast, if patterned into a line, can serve as a channel waveguide (Watanabe et al, 1996; Shi et al, 1991b) This offers the unique possibility of optical devices that can be patterned, erased, and reused In principle, these photonic circuits could be altered during device operation, enabling optical routing of optical signals (ie, optical computing) The switching of orientational order can thus be used as an all-optical switch (Shishido et al, 1997) By illuminating an azo sample with a spatially varying light pattern, birefringence gratings can also be formed (Eichler et al, 2001; Nikolova et al, 1996; Couture and Lessard, 1988).

198 198

Thus, the activity coefficient can be calculated if AGE is known; this is the difference between the work of the reversible transition of the real system at constant temperature and pressure from the standard to the actual state and the work in the same process in the ideal system: RT In Yi = ( ^) (1.3-3)

These are phase gratings, as opposed to amplitude gratings, and diffract light on the basis of spatial variation of the refractive index This is the essence of holography: two interfering coherent beams generate a spatially varying light pattern, which is encoded into the material Under illumination of the material with one of the beams, the diffraction reproduces the other encoded beam In the case of liquid crystal samples, light induces a spatial pattern of nematic and isotropic zones (which have different refractive indices) These holographic phase grating can be rapidly formed, erased, and switched (Yamamoto et al, 2001)..

As has already been mentioned, to carry out such a calculation is not a matter of thermodynamics, but requires adopting certain assumptions on the structure of the system and on interactions between particles. According to the statistical thermodynamics of solutions the logarithm of the activity coefficient for an electrolyte solution can be expanded in the series In y = <xx" + *i + yx\ + (1.3.4)

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