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The physical structure of the surface relief can be exploited to organize other systems For instance, it can act as a command layer, aligning liquid crystals (Kaneko et al, 2002; Parfenov et al, 2001, 2000; Kim et al, 2000; Li et al, 1999) The grating can be formed after the LC cell has been assembled and can be erased and rewritten Colloids can also be arranged into the grooves of an SRG, thereby templating higher order structures (Yi et al, 2002a, 2001) These lines of colloids can then be sintered to form wires (Yi et al, 2002b) The surface topography inscription process is clearly amenable to a variety of optical-lithography patterning schemes These possibilities will hopefully be more thoroughly investigated An advantage of holographic patterning is that there is guaranteed.

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S*(S1)

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registry between features over macroscopic distances. This is especially attractive as technologies move toward wiring nanometer-sized components. One example in this direction involved evaporating metal onto an SRG, and then annealing. This formed a large number of very long (several millimeter) but extremely thin (200 nm) parallel metal wires (Noel et al., 1996). Of interest for next-generation patterning techniques is the fact that the azo surface modi cation is amenable to near- eld patterning, which enables high resolution nanopatterning by circumventing the usual diffraction limit of far- eld optical systems. Proof of principle was demonstrated by irradiating through polystyrene spheres assembled on the surface of an azo lm. This results in a polarization-dependent surface topography pattern (Watanabe et al., 2000) and a corresponding surface density pattern (Ikawa et al., 2000). Using this technique, resolution on the order of 20 nm was achieved (Hasegawa et al., 2001). This process appears to be enhanced by the presence of gold nanoislands (Hasegawa et al., 2002). It was also shown that volume is not strictly conserved in these surface deformations (Keum et al., 2003). In addition to being useful as a subdiffraction limit patterning technique, it should be noted that this is also a useful technique for imaging the near eld of various optical interactions (Fukuda et al., 2001). The (as of yet not fully explained) fact that subdiffraction limit double-frequency SRGs can be inscribed via far- eld illumination (Lagugne-Labarthet et al., 2004; Labarthet et al., 2001, 2000; Naydenova et al., 1998a) further suggests the azopolymers as versatile high resolution patterning materials.

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394 bimolecular homogeneous reaction with a molecule acting as electron donor (D) or acceptor (A). In the first case, we speak about reductive quenching: S* + D ^ S ~ + D+ (5.10.3) and in the second case, about oxidative quenching: S*+A^S++A~ (5.10.4) Photoredox reactions involving excited singlet molecules, 5*(5X) are relatively rare owing to short lifetimes r0; one exception is the molecule of oxonine (oxygen analogue of thionine, see below) possessing relatively long singlet lifetime (2.4 ns) and also small quantum yield of a non-radiative Sl-^ 7i conversion (intersystem crossing), about 3 10~3. Oxonin, therefore, reacts photochemically, e.g. with Fe 2+ via the excited singlet state. Figure 5.57 demonstrates that the photoexcited molecule S* exhibits, in both spin states, a lower ionization potential (IP*) and a higher electron affinity (EA*) in comparison with that of the ground state 5 molecule (IP, EA). Consequently, the photoexcited molecule 5* is a better oxidizing as well as reducing agent than the ground state molecule, S. Neglecting the entropy and pressure changes, we can express the relative change of the standard redox potential of the S/S~ couple as follows: E0(S/S~) - E0(S*/S~) = -(AG - ^G*)|F - -ejF and analogously: E (S+/S) - E (S+/S*) - ejF (5.10.6) ex is the excitation energy of 5 (mostly of the first triplet state, S*{TX)). The actual changes of the redox potentials introduced by photoexcitation are dramatic (cf. Table 5.6). Thus, the photoexcited molecule S* is a powerful redox reactant to drive various unusual redox reactions in the electrolyte.

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Table 5.6 Properties of three typical photoredox-active molecules, bpy denotes 2,2' bipyridine, TMPP is tetra Nmethylpyridine porphyrin; Amax is the wavelength of the absorption maximum, e is the extinction coefficient at Amax, cpT is the quantum yield of the formation of the excited triplet state, r0 is its lifetime, and EQ are standard redox potentials Thionine*

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