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231 surfactant and ox is the surface charge for complete coverage of the electrode by the surfactant. The described adsorption phenomena are characteristic for electrodes of sp metals. Transition metal electrodes are usually connected with irreversible chemisorption phenomena, discussed in Section 5.7. References Barlow, C. A., and J. R. MacDonald, Theory of discreteness of charge effects in the electrolyte compact double layer, AE, 6, 1 (1967). Damaskin, B. B., and V. E. Kazarinov, The adsorption of organic molecules, CTE, 1, 353 (1980). Damaskin, B. B., O. A. Petrii, and V. V. Batrakov, Adsorption of Organic Compounds on Electrodes, Plenum Press, New York, 1971. Frumkin, A. N., and B. B. Damaskin, Adsorption of organic compounds at electrodes, MAE, 3, 149 (1964). Grahame, D. C , see page 203. Henderson, D., L. Blum, and M. Lozada-Cassou, The statistical mechanics of the electrical double layer, /. Electroanal. Chem., 150, 291 (1983). Kornyshev, A. A., W. Schmickler, and M. A. Vorotyntsev, Phys. Rev. B, 25, 5244 (1982).

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31 system used. If the volume element dV contains dNt ions of sort / with charge ztet the space charge density p, formed by ions of sort / is given as A=^ , (1.3.7)

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Probably, there is no other molecule as azobenzene that has been so well known for a long time and, nevertheless, still brings off surprising phenomena. Though azobenzene once started off as a simple dye a molecule just absorbing light it has been recognized as photochrome, a molecule changed by light and has since become indispensable in optics as a molecule controlling light. Recently, it has revealed a completely different characteristic a molecule moved by light. The combination of all these properties in one molecule makes it favored for a wide range of optical applications. The application of azobenzenes is further supported by the availability of various commercial dyes or by simplicity of their synthesis. Different material aspects and optical applications of azobenzene may be found in some recent reviews (Seki, 2007; Shibaev et al., 2003, 1996; Natansohn and Rochon, 2002; Yager and Barrett, 2001; Viswanathan et al., 1999; Fuhrmann and Wendorff, 1997; Ichimura, 1996; Ichimura et al., 1994). Most azobenzene derivatives can be isomerized reversibly between the E and Z isomeric forms by light or heat. Some derivatives may show phototautomerism, photodimerization, photoreduction, and fading. The effects discussed in this chapter are based on E Z photoisomerization of aromatic azobenzenes (Rau, 1990) also known in the literature as trans cis photoisomerization. Photoisomerization reaction of azobenzene allows the reversible change of molecular properties such as absorbance, dipole moment, polarity, geometric shape, and others. These molecular changes may be used to control macroscopic properties of materials. For example, the change of the geometric form of

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If the origin of the coordinate system is located in the centre of the central A:th ion, the number of particles dTV, in the volume dV is given by a distribution function, expressed by Debye and Hiickel in terms of the Boltzmann distribution law (cf. p. 215) dA/i = Nt exp (

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(1.3.8)

molecules can affect the formation of molecular aggregates (Stumpe et al, 1996; Shimomura, 1993), induce phase transitions in the material (Hasegawa et al, 1999), or change the enzyme activity (Willner et al, 1991) Recently, the photoinduced change of the geometric shape of macroscopic objects has been demonstrated (Ikeda et al, 2007; Bublitz et al, 2000; Seki et al, 1996) If the irradiating light activates both E Z and back Z E transitions, the steady state of photoreaction is established, whereas the molecules undergo repeated isomerization cycles In many cases, it is not an equilibrium concentration of both isomeric forms that is important, it is the light-induced dynamics, that is, the continuing movement of the chromophore.

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Here, k is the Boltzmann constant and Nt = N;/V is the total number of ions of sort i divided by the total volume. Thus (:^)

In other words, the isomerizing azobenzene molecule works as a light-driven molecular motor, whose power and force direction may be controlled by the parameters of the irradiating light, such as wavelength, polarization, or intensity distribution This statement is kept in mind when discussing the photoinduced processes in this chapter The irradiation with polarized light results in the preferential orientation of azobenzene molecules perpendicularly to the light electric eld vector orientational order is induced, the system becomes anisotropic The photoinduction of molecular order causes plenty of macroscopic effects, including optical anisotropy, which is one of the subjects in this chapter After the actinic light is switched off, the photoproduct reacts back to the thermally stable E isomeric form and the initial state is restored at the molecular level It may be changed thermally or by irradiation with actinic light.

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