Reaction field volume, electron transfer

Volume 2 is dedicated to a detailed description of the most important classes of electron transfer reactions involving organic molecules (Part 2.1) and organometallic and inorganic compounds (Part 2.2). In several cases the reactions described are important not only from the viewpoint of fundamental research on reaction mechanisms, but also for their catalytic and synthetic applications. The emerging fields of electron transfer reactions of fullerenes, electron-reservoir complexes, and biomi-metic electron transfer chemistry of porphyrins are discussed in depth. 

In Chapter 11, Molecular Electron Transfer, the broad and deep field of electron-transfer reactions of metal complexes is surveyed and analyzed. In Chapter 12, Electron Transfer From the Molecular to the Nanoscale, the new issues arising for electron-transfer processes on the nanoscale are addressed this chapter is less a review than a toolbox for approaching and analyzing new situations. In Chapter 13, Magnetism From the Molecular to the Nanoscale, the mechanisms and consequences of magnetic coupling in zero- and one-dimensional systems comprised of transition-metal complexes is surveyed. Related to the topics covered in this volume are a number addressed in other volumes. The techniques used to make the measurements are covered in Section I of Volume 2. Theoretical models, computational methods, and software are found in Volume 2, Sections II and III, while a number of the case studies presented in Section IV are pertinent to the articles in this chapter. Photochemical applications of metal complexes are considered in Volume 9, Chapters 11-16, 21 and 22. 

In the last decade, an intense and successful investigation of this phenomenon has focused on its mechanism. The experimental facts discovered and the debate of their interpretation form large portions of these volumes. The views expressed come both from experimentalists, who have devised clever tests of each new hypothesis, and from theorists, who have applied these findings and refined the powerful theories of electron transfer reactions. Indeed, from a purely scientific view, the cooperative marriage of theory and experiment in this pursuit is a powerful outcome likely to oudast the recent intense interest in this field. 

Although a previous chapter in this volume provides a broader perspective on the reactivity of radical cations, in this section we will examine intramolecular electron-transfer reactions coupled with or followed by cleavage of a bond in odd electron species such as radical cations, radical zwitterions and radical anions. In particular, this paragraph will be divided in oxidative and reductive bond-cleavage processes. Because this field is however too large to be covered extensively here, the discussion will be limited to selected examples—for oxidative cleavages, side-chain fragmentation reactions of alkylaromatic radical cations and decarboxylation reactions of radical zwitterions derived from benzoic and arylalkanoic acids, and for reductive... 

This first chapter to Volume 2 Interfadal Kinetics and Mass Transport introduces the following sections, with particular focus on the distinctive feature of electrode reactions, namely, the exponential current-potential relationship, which reflects the strong effect of the interfacial electric field on the kinetics of chemical reactions at electrode surfaces. We then analyze the consequence of this accelerating effect on the reaction kinetics upon the surface concentration of reactants and products and the role played by mass transport on the current-potential curves. The theory of electron-transfer reactions, migration, and diffusion processes and digital simulation of convective-diffusion are analyzed in the first four chapters. New experimental evidence of mechanistic aspects in electrode kinetics from different in-situ spectroscopies and structural studies are discussed in the second section. The last... 

The general principles of electrochemistry are presented in reviews, books, and many ongoing series of reviews of "Advances in the Field". In regard to electroorganic chemistry, a useful introduction to the necessary concepts are the books by Fry nd a number of others. Scale-up for practical applications is addressed in a primer and further described in a more extensive volume on industrial electrochemistry. Electrochemical reactions in which a key process is the transfer of electrons at an electrode can be classified in three general types. 

---