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Applications, Oxford University Press, Oxford, 1982. Boguslavsky, L. I., Insulator/electrolyte interface, CTE, 1, 329 (1980). Butler, J. A. V., see page 202. Gaal, O., G. Medgyesi, and L. Vereczkey, Electrophoresis in the Separation of Biological Macromolecules, John Wiley & Sons, New York, 1980. Gerischer, H., Semiconductor electrode reactions, AE, 1, 31 (1961). Gerischer, H., Electrochemical photo and solar cells. Principles and some experiments, /. Electroanal. Chem., 58, 263 (1975). Green, M., Electrochemistry of the semiconductor-electrolyte interface, MAE, 2, 343 (1959). Hunter, R. J., The double layer in colloidal systems, CTE, 1, 397 (1980). Lyklema, J., The electrical double layer on oxides, Croatica Chem. Acta, 43, 249 (1971). Maredek, V., Z. Samec, and J. Koryta, Electrochemical phenomena at the interface of two immiscible electrolyte solutions, Advances in Interfacial and Colloid Science, 29, 1 (1988).

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Figure 1.4. The mechanism of azobenzene isomerization proceeds either via rotation or inversion. The cis state has the phenyl rings tilted at 901 with respect to the CNNC plane.

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Electrodes, Plenum Press, New York, 1980. Myamlin, V. A., and Yu. V. Pleskov, Electrochemistry of Semiconductors, Plenum Press, New York, 1967. Pleskov, Yu. V., Electric double layer on semiconductor electrode, CTE, 1, 291 (1980). Samec, Z., The electrical double layer at the interface of two immiscible electrolyte solutions, Chem. Revs, 88, 617 (1988). Spaarnay, M. J., see page 203. Vanysek, P., see page 191. Verwey, E. J. W., and J. Th. G. Overbeek, Theory of the Stability of Lyophobic Colloids, Elsevier, Amsterdam, 1948.

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and Tahara, 2000). In contrast, Ho et al. (2001) found evidence that the pathway is compound-speci c: a nitro-substituted azobenzene photoisomerized via the rotation pathway. Furthermore, ab initio and density functional theory calculations indicate that both pathways are energetically accessible, although inversion is preferred (Angeli et al., 1996; Jursic, 1996). Thus, both mechanisms may be competing, with a different one dominating depending on the particular chromophore and environment. The emerging consensus nevertheless appears to be that inversion is the dominant pathway for most azobenzenes (Ikeda and Tsutsumi, 1995). The availability of the inversion mechanism explains how azos are able to isomerize easily even in rigid matrices, such as glassy polymers, since the inversion mechanism has a much smaller free volume requirement than rotation. The thermal back-relaxation is generally rst order, although a glassy polymer matrix can lead to anomalously fast decay components (Barrett et al., 1995, 1994; Paik and Morawetz, 1972; Priest and Sifain, 1971), attributed to a distribution of chromophores in highly strained con gurations. Higher matrix crystallinity increases the rate of decay (Sarkar et al., 2001). The decay rate can act as a probe of local environment and molecular conformation (Tanaka et al., 2004; Norman and Barrett, 2002). The back-relaxation of azobenzene is acid catalyzed (Rau et al., 1981), although strongly acidic conditions will lead to side reactions (Hartley, 1938). For the parent azobenzene molecule, quantum yields (which can be indirectly measured spectroscopically (Shen and Rau, 1991; Priest and Sifain, 1971; Malkin and Fischer, 1962) are on the order of 0.6 for the trans-cis

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In the case of electrodes with low overpotential the process of molecular hydrogen evolution is particularly more complicated than with electrodes showing high overpotential where a single assumption of slow discharge step could successfully elucidate all experimental results. It can be taken for sure, however, that in the case of electrodes with low overpotential it is necessary to consider, as a slow step, the process of removal of molecular hydrogen from the electrode together with the discharge process. A. N. Frumkin, V. S. Bagotzky, and Z. A. Iofa, 1952 5.1 Basic Concepts and Definitions

PVS, or PSS or rather exotic ones like chitosan, carragenan, cyclodextrine, or dendritic polyelectrolytes have been employed LbL layers with low-molecularweight azobenzene species could be considered as analogue of typical materials used for photoorientation and photoinduced mass transport, namely, azobenzene side-chain polymers In this case, covalent bonding of azobenzene moieties and polymer is replaced with ionic interactions (weak or strong depending on the type of polyelectolyte) (compare Fig 22b and d) The above-mentioned restriction to the structure of azodye is also of crucial importance to resulting photochemical properties Namely this causes a restriction on the freedom of movement of the azobenzene species, which seems to be of particular importance for the photoinduced mass transport Depending on the number of charged groups and polyelectrolyte type, these restrictions would be more or less pronounced Photoisomerization has been investigated for some of these solid-state complexes.

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