Nonlinear response, electron-transfer

The simplest electrodimerization mechanism occurs when the species formed as the result of a first electron transfer reaction reacts with itself to form a dimer (Scheme 2.7). This mechanism is usually termed radical-radical dimerization (RRD) because the most extensive studies where it occurs have dealt with the dimerization of anion and cation radicals formed upon a first electron transfer step as opposed to the case of radical-substrate dimerizations, which will be discussed subsequently. It is a bimolecular version of the EC mechanism. The bimolecular character of the follow-up reaction leads to nonlinear algebra and thus complicates slightly the analysis and numerical computation of the system. The main features of the cyclic voltammetric responses remain qualitatively similar, however. Unlike the EC case, however, the dimensionless parameter,... 

K. Ando and S. Kato, Dielectric relaxation dynamics of water and methanol solutions associated with the ionization of /V,/V-dimcltiylanilinc theoretical analyses, J. Chem. Phys., 95 (1991) 5966-82 D. K. Phelps, M. J. Weaver and B. M. Ladanyi, Solvent dynamic effects in electron transfer molecular dynamics simulations of reactions in methanol, Chem. Phys., 176 (1993) 575-88 M. S. Skaf and B. M. Ladanyi, Molecular dynamics simulation of solvation dynamics in methanol-water mixtures, J. Phys. Chem., 100 (1996) 18258-68 D. Aheme, V. Tran and B. J. Schwartz, Nonlinear, nonpolar solvation dynamics in water the roles of elec-trostriction and solvent translation in the breakdown of linear response, J. Phys. Chem. B, 104 (2000) 5382-94. 

The use of photoinduced electron transfer to enhance the nonlinear optical response of semiconducting polymers is summarized in Section VF the use of photoinduced electron transfer to enhance the response of polymer photodetectors and photovoltaic cells is summarized in Section VII. 

Overlapping bands can become a problem when, for example, there are two consecutive electron-transfer reactions [137]. One solution is to look at the time-or potential-resolved spectra [138], Overlapping bands are often responsible for nonlinear Nemstian plots in OTTLE studies [139]. There are only a few examples of the use of differentiating the absorbance [134], least-squares analysis [140], of the latest chemometric techniques [141]. In the latter study, evolutionary factor analysis of the spectra arising from the reduction of E. coli reductase hemoprotein (SiR-HP ) in which three species are present and the reduction of the [Cl2FeS2MoS2FeCl2] (four species present). The most challenging part of the work was the determination of the transformation matrix. 

Mark A. Ratner (Co-Chair) is professor of chemistry. Department of Chemistry, Northwestern University, Evanston, Illinois. He obtained his B.A. from Harvard University (1964) and his Ph.D. (chemistry) from Northwestern University (1969). His research interests are in nonlinear optical response properties of molecules, electron transfer and molecular electronics, dynamics of polymer electrolyte transport, self-consistent field models for coupled vibration reaction dynamics, mean-field models for extended systems, and tribology and glassy dynamics. He has some 312 professional publications. Ratner is a fellow of the American Physical Society and the American Association for the Advancement of Science and has received numerous teaching awards from Northwestern University. He is a member of the National Academy of Sciences. 

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