Photochemistry II: Electron Transfer Kinetics

This lecture delves into the dynamics of electron transfer reactions in photochemistry, focusing on the nuclear reorganization-controlled kinetics. It covers the Marcus-Levich theory, the formation of precursor complexes, and the geometrical derivation of the Marcus equation. The discussion extends to Marcus-Hush theory, the avoided crossing of potential energy surfaces, and the Marcus vs. Tafel equation. Additionally, it explores adiabatic vs. diabatic electron transfer processes, the nuclear reorganization energy, and Fermi's golden rule for diabatic electron transfer. Practical applications and theoretical implications are thoroughly examined.

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Electrochemical kinetics is the field of electrochemistry that studies the rate of electrochemical processes. This includes the study of how process conditions, such as concentration and electric potential, influence the rate of oxidation and reduction (redox) reactions that occur at the surface of an electrode, as well as an investigation into electrochemical reaction mechanisms.

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Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data for a voltammetric experiment comes in the form of a voltammogram which plots the current produced by the analyte versus the potential of the working electrode. Voltammetry is the study of current as a function of applied potential.

Overpotential

In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically-determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts.

Phase transition

In chemistry, thermodynamics, and other related fields, a phase transition (or phase change) is the physical process of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic states of matter: solid, liquid, and gas, and in rare cases, plasma. A phase of a thermodynamic system and the states of matter have uniform physical properties. During a phase transition of a given medium, certain properties of the medium change as a result of the change of external conditions, such as temperature or pressure.

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