Self-exchange charge transfer

Fig. 36.26. Self-exchange charge transfer in biphenyl oligomers.

Electric conduction can also be carried out by a hopping mechanism between adjacent redox sites. This mode of self-exchange charge transfer within silicate composite was exploited by the incorporation of redox polymers such as the osmium redox polymer, [Os(bpy)(2)(PVP)(10)Cl]Cl in the silicate [101], A similar approach based on the creation of naphthoquinone-modified silicate CCE was also demonstrated by Rabinovich et al. [47], Here, the binder itself functions as a charge transfer polymer due to the presence of pendant quinone functionalities. 

The self-exchange electron-transfer (SEET) process, in which a radical is trapped by the parent molecule, has been studied using the intersecting-state model (ISM).91 Absolute rate constants of SEET for a number organic molecules from ISM show a significant improvement over classical Marcus theory92-94 in the ability to predict experimental SEET values. A combination of Marcus theory and the Rips and Jortner approach was applied to the estimation of the amount of charge transferred in the intramolecular ET reactions of isodisubstituted aromatic compounds.95... 

At the microscopic level, polaron hopping can be viewed as a self-exchange electron-transfer reaction where a charge hops from an ionized oligomer or chain segment to an adjacent neutral unit. In the framework of semiclassical Marcus theory, the electron-transfer rate is written as... 

Blue copper proteins, 36 323, 377-378, see also Azurin Plastocyanin active site protonations, 36 396-398 charge, 36 398-401 classification, 36 378-379 comparison with rubredoxin, 36 404 coordinated amino acid spacing, 36 399 cucumber basic protein, 36 390 electron transfer routes, 36 403-404 electron transport, 36 378 EXAFS studies, 36 390-391 functional role, 36 382-383 occurrence, 36 379-382 properties, 36 380 pseudoazurin, 36 389-390 reduction potentials, 36 393-396 self-exchange rate constants, 36 401-403 UV-VIS spectra, 36 391-393 Blue species... 

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