Laser Electrochemistry of Intermediates

Laser photoelectron emission not only allows investigation of interfaces between electrodes and solution, but also provides a method for fast generation of intermediate species in the vicinity of the interface and so permits study of their electrode reactions. Laser Electrochemistry of Intermediates presents the first-ever comprehensive review of this important phenomenon and its electrochemical applications. The book explores how the innovative method of laser electron emission from metal electrodes resolves two fundamental problems inherent in current methods of intermediate species (IS) generation and detection: difficulty generating IS quickly in the vicinity of the electrode surface and low IS surface concentration. In addition, for the first time, quasi-free and solvated electrons, hydrogen atoms, simple organic and inorganic radicals, and ions with anomalous valence are systematically studied. Laser Electrochemistry of Intermediates incorporates a unique, two-pronged analytical approach. First, the authors consider the kinetics and thermodynamics of the processes based on the participation of IS in its one-electron stages, thus allowing the assignment of real physical meaning to the electrochemical measurables. Second, they consider electrode reactions side by side with homogeneous reactions of electron transfer, facilitating understanding of the universal theory of electron transfer reactions in polar media as well as the peculiarities of these reactions occurring in the interface between electrode and solution.

Victor A. Benderskii, Alexander V. Benderskii

PrefaceElectron Emission from Metal into Electrolyte SolutionOne-Photon Emission. Theoretical Model. Two-Photon Emission. Thermoemission of Nonequilibrium Heated Electron Gas.Excess Electrons in Polar LiquidsThermalization Length. Energy Losses by Photoelectrons. Solvation of Excess Electrons. Solvation Dynamics. Thermodynamic Properties of Excess Electrons.Electron Transfer ReactionsPolarization Coordinate. Dynamic Polarization of Dielectric Continuum. Adiabatic and Non-Adiabatic Reactions. Reorganization Energy and Electronic Matrix Element. Energy Gap Law. Molecular Dynamics of Electron-Transfer Reactions.Regimes of Electrode ReactionsTunneling Current from Metal into Redox Center. Normal, Barrierless and Activationless Discharge. Modified Arrhenius Law. Electronic Friction. Parabolic Marcus' Formula and Tafel Law.Time Resolved Voltammography of Intermediate SpeciesGeneration of Short-Lived IS. Discharge Currents of IS Generated by Electron Emission. Voltammograms of IS Generated by Alternating Photoemission Current. Discharge of IS Generated by Short Photoemission Pulse. Time-Resolved Voltammograms of IS. Characteristic Quadrangle of Tafel Lines for Two-Electron Electrode Reactions.Electrochemistry of Hydrogen AtomsAnomalous Mobility of H Atoms in Water. Ionization of Hydrogen Atoms. Electrochemical Desorption. Electron-Proton Transfer.Electrochemistry of Free Radicals and Ions of Anomalous Valence IS of Electrochemical Carbon Cycle. Electrochemistry of Alkyl and Hydroxyalkyl Radicals. pKa Scale of Weak CH-Acids. IS of the Electrochemical Nitrogen Cycle. Electrode Reactions of Ions of Anomalous Valence. ConclusionBibliographyIndex