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Figure 2.9. Optical anisotropy induced by the light in a lm of the compound Alizarin Yellow GG-PEI: kinetics of the parallel (dashed black line) and orthogonal (solid gray line) polarization components of the transmitted probe beam. (a) Induction and relaxation, solid black line presents two-exponential decay t to the data, and (b) switching by alternation of polarization of the irradiating beam. Source: Kulikovska et al., 2007. Reproduced with permission from American Chemical Society.

Fig. 5.1 Transfer of an electron (or a hole) between the electrode and the electroactive substance in solution. (According to H. Gerischer)

Figure 2.10. Chemical structure of complexes of poly(vinyl-N-alkylpyridinium) with Methyl Orange and the Ethyl Orange (EO) with C12D and C16D surfactants.

i.e. by polarizing the electrode to the potential E + AE) can shift eF to higher or lower energies. If F is shifted towards the occupied level in Ox! (that is Aj is negative), then reduction of Oxl is made easier and oxidation (> of Redi becomes more difficult (or even completely impossible if eF is shifted sufficiently above the energy of Red t ). A decrease in eF (through a positive A0) towards the occupied level in Red2 has the opposite effect. Obviously, oxidation and reduction occur simultaneously in the vicinity of the equilibrium potential (where the Fermi levels in the metal and solution are close to one another). Conditions are somewhat more complicated at semiconductor electrodes. In contrast to metal electrodes, where the donor and acceptor levels are concentrated in a single energy band, the Fermi level for semiconductors lies in the forbidden band (see Figs 2.3 and 3.2), where there are no electron energy levels. Consequently, in the vicinity of the equilibrium potential where the electrochemical potentials of the electrons in solution and in the metal (i.e. the Fermi level) are identical, no charge transfer occurs (provided that there are no electronic surface states at the interface; see Section 4.5.1). Charge transfer requires a large change in A0, where the occupied electronic level in Red attains the level of the conductivity band in the semiconductor or the unoccupied level in Ox attains the level of the valence band. It should be recalled that the electrons and holes participate in charge transfer in the vicinity of the semiconductor-electrolyte interface,

No (open interfaces to higher level mgt)

The maximum value of photoinduced birefringence achieved were 0067 and 031 for ethyl- and methyl-quaternized polyvinylpyridine (see Fig 210a), respectively (Zhang et al, 2008; Xiao et al, 2007) The authors believe that such a great difference in photoorientation properties is hardly attributed to structural difference consisting of one methylene group, but more probably to the difference in synthesis, puri cation, lm preparation, etc A rather simple approach for design of low-molecular-weight ionic supramolecular complexes has been recently proposed (Zakrevskyy et al, 2005, 2004; Guan et al, 2003) These new materials are formed by introduction of oppositely charged ions between different low molecular tectonic units and are called ISA complexes In contrast to the discussed LbL and polyelectrolyte-based ionic complexes, the polymer unit is usually replaced by low-molecular-weight surfactant.

249 where their energy is different from that in the bulk of the semiconductor as a result of band 'bending' (see Sections 451 and 5104) Conditions at the interface between two immiscible electrolyte solutions (ITIES) are analogous to those at the electronic conductor-electrolyte interface The charge carriers passing across the interface are primarily ions and they are transferred to a region where they have a lower electrochemical potential The transfer of electrons from the species Redj in one phase requires that the second phase contain the species Ox2 with an unoccupied acceptor level with similar or lower energy compared with the donor level in Redx A change in the electrochemical potential of the ions or electrons can be achieved through a change in the potential difference between the two phases.

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The presence of a concentration gradient of electroactive substances at the phase boundary between the electrode and the solution or between two electrolytes, the presence of an electric field and, finally, the effect of mechanical forces all lead to transport processes, described in 2 It should be pointed out that investigations in electrochemical kinetics are usually carried out with solutions containing an excess of indifferent electrolyte compared to the electroactive substance, to exclude the effect of migration The rule for the equivalence between the material flux of the charged species and the electric current (Eq 2314) is a general formulation of the Faraday law In its classical form, this rule is connected with a special case, ie material flux through the electrode-solution interface In this special case the Faraday law deals with equivalence between the material yield in an electrode reaction and the charge passed: 1.