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Chemical Dynamics in Condensed PhasesRelaxation, Transfer and Reactions in Condensed Molecular Systems$
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Abraham Nitzan

Print publication date: 2006

Print ISBN-13: 9780198529798

Published to Oxford Scholarship Online: November 2020

DOI: 10.1093/oso/9780198529798.001.0001

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PRINTED FROM OXFORD SCHOLARSHIP ONLINE (oxford.universitypressscholarship.com). (c) Copyright Oxford University Press, 2021. All Rights Reserved. An individual user may print out a PDF of a single chapter of a monograph in OSO for personal use. date: 08 December 2021

Electron Transfer Processes

Electron Transfer Processes

(p.552) 16 Electron Transfer Processes
Chemical Dynamics in Condensed Phases

Abraham Nitzan

Oxford University Press

Electron transfer processes are at the core of all oxidation–reduction reactions, including those associated with electrochemistry and corrosion. Photoelectrochemistry and solar energy conversion, organic light emitting diodes, and molecular electronic devices, all dominated by electron transfer and electron transmission in molecular systems, are presently subjects of intensive research at the interface of science and technology. Similarly, electron transfer processes constitute fundamental steps in important biological phenomena such as photosynthesis and vision. This chapter is an introduction to the general phenomenology and theoretical concepts associated with these processes. Electron transfer is one of the most important, and most studied, elementary chemical processes. This most fundamental oxidation–reduction process lies at the core of many chemical phenomena ranging from photosynthesis to electrochemistry and from the essential steps governing vision to the chemical processes controlling corrosion. As other molecular phenomena that involve charges and charged particles, the natural environment for such processes is a polar solution; the solvation energy associated with the polarization of the environment is a major component in the energetics of such processes. Noting that in vacuum typical molecular ionization potentials are of the order of (100–400)kBT for T = 300 K, it appears that the stabilization of ionic species by the solvent environment is the reason why electron transfer processes in solution can take place at room temperature. When we try to go beyond this general statement, questions arise.

Keywords:   Arrhenius behavior, Condon approximation, Marcus parabolas, Poisson equation, Reorganization energy, cross electron transfer reaction, detailed balance, electron transfer processes

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