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Given that e0=8.854 10 12C2/(Nm2), jwj % 1 and z0=377 O, and using the typical values I=100 mW/cm2 and l=488 nm, a force density of B100 N/m3 is obtained. Not only are these two orders of magnitude smaller than the force of gravity (which itself is presumably negligible), but they also fall short of the estimated 1011 1014 N/m3 necessary for mass transport in polymer lms to occur (Saphiannikova et al., 2004a).

1 1 1 1

For instance, how are these geographically separate computers supposed to trust each other, especially in today s climate of hacking and viruses This special case of clustering is the basis for grid computing..

One of the rst mechanisms to be presented was the suggestion by Barrett et al. (1998, 1996) about pressure gradients inside the polymer lm. The assumption is

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that azobenzene isomerization generates pressure both because of the greater free volume requirement of the cis and the volume requirement of the isomerization process itself Isomerization of the bulky chromophores leads to pressure that is proportional to light intensity The light intensity gradient thus generates a pressure gradient, which of course leads to material ow in a uid mechanics treatment Order-of-magnitude estimates were used to suggest that the mechanical force of isomerization would be greater than the yield point of the polymer, enabling ow Plastic ow is predicted to drive material out of the light, consistent with observations in amorphous systems At rst it would seem that this mechanism cannot be reconciled with the polarization dependence, since the pressure is presumably proportional to light intensity, irrespective of its polarization state However, one must more fully take orientational effects into account.

Like many of the technologies discussed in this book, grid (or utility) computing is a technology that is still evolving. However, it is fast on its way to realizing the vision of large-scale resource-sharing across geographically dispersed

Fig. 5.56 Triangular-pulse voltammograms of oxidation of 0.1 M formic acid in 0.5 M H2SO4 at various faces of a single-crystal platinum electrode, 22 C, dE/dt = 50 mV s"1. (According to C. Lamy) potential range where the Kolbe reaction proceeds can be explained in two ways. The anion of the fatty acid or an oxidation intermediate may block the surface of the electrode (cf. page 361), or as a second alternative, the acid may react with an intermediate of anodic oxygen evolution, which then cannot occur. The mechanism of this interesting process has not yet been completely elucidated; the two main hypotheses are illustrated in the following schemes: RCOO--*RCOOadsRCOO a d s "-> RCOO a d s + e RCOO a d s ->R a d s + CO 2 (5-9-7) Rads"* products, for example R 2

Linearly polarized light addresses fewer chromophores than circularly polarized light and would thus lead to lower pressure Thus, pure polarization patterns can still lead to pressure gradients Combined with the fact that the polarized light is orienting (and in a certain sense photobleaching), this can explain some aspects of the polarization data The agreement, however, is not perfect For instance, the (s, s) and ( p, p) combinations lead to very different gratings in experiments It is possible that some missing detail related to polarization will help explain this discrepancy Combining a variety of results from the literature, it now appears that the mechanical argument of a pressure mechanism may be correct In one experiment, irradiation of a transferred Langmuir Blodgett lm reversibly generated B5 nm hills, attributed to nanoscale buckling that relieves the stress induced by lateral expansion (Matsumoto et al, 1998).

RCOCT RCOCT + 2e > R + CO2 + e > R+ + CO2 (598) further products Similarly as for other chemical reactions, the activation energy for the electrode reactions of organic substances depends on the nature and position of the substituents on the aromatic ring of an organic molecule As the standard potentials are not known for many of these mostly irreversible processes and as they were mainly investigated by polarography, their basic data is the half-wave potential (Eq 5427) The difference of the half-wave potential of the tested substance, i, and of the reference substance (which is, for example, non-substituted) for the same type of electrode reaction (eg nitrogroup reduction) is given by the equation RT k^ Ew - i/2,ref = AE1/2 = AE0' + - In - ^ (59.

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This result is conspicuously similar to the spontaneous polarization-dependent formation of hexagonally arranged B500 nm hills seen on an amorphous azopolymer sample irradiated homogeneously (Hubert et al, 2002a,b) In fact, homogeneous illumination of azo surfaces has caused roughening (Mechau et al, 2002), and homogeneous optical erasure of SRGs leads to similar pattern formation (Lagugne-Labarthet et al, 2002) The early stages of SRG formation, imaged by AFM, again show the formation of nanosized hills (Henneberg et al, 2001a) Taken together, these seem to suggest that irradiation of an azo lm leads to spontaneous lateral expansion, which induces a stress that can be relieved by buckling of the surface, thereby generating surface structures In the case of a light gradient, the buckling is relieved by mass transport coincident with the light eld that generated the pressure inside the lm.