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331 of metals or semiconductors on glass or polymer supports play a key role in these investigations. Alternatively, very fine, transparent metal mesh can be used as an electrode. Absorption spectra can be advantageously studied by means of a working electrode in a thin-layer system (with a thickness of about 0.05-0.5 mm), where electrolysis of all the bulk electrolyte lasts only a few seconds (thin-layer spectroelectrochemistry). Under certain conditions, the product of the electrode process can be studied by using electrochemically generated luminescence. This phenomenon occurs when the reactants generated at the electrode or in a subsequent chemical reaction have such high free energy that they can interact to form products in electronically excited states. If these states are capable of radiative relaxation, then they can be identified according to their luminescence spectra. Reactants for luminescence studies can be generated in two ways, either subsequently on a single electrode polarized, e.g. by a rectangular or sinusoidal voltage, or simultaneously, e.g. at a rotating ring disk electrode. Electrochemically generated luminescence finds wide application in the study of organic substances and radicals and also of some complexes of transition metals (for example, Ru(bpy) 3 2+ , where bpy = bipyridine). This method is especially useful in determining the mechanisms of electrochemical processes. The most important methods used in in-situ studies of electrode surfaces are various modifications of reflection spectroscopy in the ultraviolet through infrared regions. For electrochemical applications, the specular reflection (at smooth electrode surfaces) is much more important than the diffuse reflection from matt surfaces. The reflectivity, R, of the electrode/ electrolyte interface is defined by: R=I/I0 (5.5.41)

An excess doping of chiral dopant into a compensated nematic phase breaks the compensated state, and consequently produces a helical structure again.

where Io is the intensiy of incident radiant energy, and / is the intensity of that reflected from the interface (some authors distinguish the term 'reflectivity' for specular reflection and 'reflectance' for diffuse reflection.) Specular reflection of electromagnetic radiation at the (electrochemical) interface is generally described by Fresnel equations. Supposing the most simple case that both the electrolyte and electrode are transparent and differ only in their refractive indexes, nx and n2, the reflectivity for normal incidence of the radiation equals: R = [(n2-n1)/(n2 + nl)]2 (5.5.42)

Partitioning of the system resources, either through hardware or software, is another approach for disaggregation within a single system. Either partitioning method creates multiple isolated servers, or partitions. Each partition is allocated one or more CPUs, a physical memory block, and specific I/O paths, and runs its own instance of the operating system. Resources are owned by the partition, without any sharing across partitions. Depending on the implementation, there may be the ability to have dynamic partitioning such that resources may be added to, moved to, and removed from a partition. Partitioning assumes all partitions run the same OS.

0.8 mm 0.8 mm (a) (b)

and R = 1 for grazing incidence. At other angles of incidence 0 < 6 <90 , the reflectivity of radiation polarized normal and parallel to the plane of reflection is different, the former increases monotonously from value given by Eq. (5.5.42) to unity, but the latter goes through minimum at angle 6h (so called Brewster angle): 0 b = arctan {n2lnx). (5.5.43)

Figure 10.19. (a) Gray mask and (b) Color patterning of the Ch LC containing E44, m-azo-8, and chiral obtained by UV irradiation for 10 s through the gray mask at 251C. Source: Yoshioka et al., 2005. See color insert.

8

The approximate picture of a transparent electrochemical interface is rather far from the actual situation Nevertheless, the Fresnel equations are valid also for absorbing media, if one uses the complex refractive indexes, Nk: Nk = nk-i(aX/4jz), k = l,2 (5544) (or is absorption coefficient of the medium and A wavelength) In this case, Eq (5542) is replaced by R = [(n- I) 2 + n2a2X2/Sjt2]/[(n + I) 2 + n2a2X2l%n2\ (5545) where n=njn2 is the relative refractive index Equation (5545) demonstrates the fact that strongly absorbing materials, like metals, are also strongly reflecting, with / 1 even at the normal incidence The most important situation occurs when a film of different optical properties is formed at the electrode surface.

UV Vis,

In this case, theory predicts that the R value can be changed, even for non-absorbing films, as a result of existence of a third phase with different refractive index interspaced between the electrode and electrolyte Therefore, the entire observed decrease in reflectivity R is not necessarily caused by the absorption of radiation in the film This approximation, is, however, reasonably acceptable when the film is supported by a highly reflective phase, such as smooth metal electrode In general, two basic experimental arrangements of reflective spectroelectrochemistry are possible: (a) The excitation beam passes first through a window in the electrochemical cell, then through the electrolyte and is finally reflected from the surface of the electrode back into the electrolyte phase (specular external reflectance) There is a sufficient number of suitable substances for the preparation of electrodes, electrolytes and windows for working in the ultraviolet and visible regions.