Abstract
Chemical and electrochemical reactions in condensed phases are generally quite complex processes, but outer-sphere electron-transfer reactions are sufficiently simple that we have reached a fair understanding of them in terms of microscopic concepts. In this chapter we give a simple derivation of a semiclassical theory of outer-sphere electron-transfer reactions, which was first systematically developed by Marcus [1] and Hush [2] in a series of papers. Several of the concepts that we develop here play also a role in electrocatalysis.
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Notes
- 1.
Really this includes the inner sphere as well, but for brevity we shall subsume it under the general term solvent
- 2.
We use the usual symbol ε for the dielectric constant; no confusion should arise with the energy variable employed
References
R.A. Marcus, J. Chem. Phys. 24 (1956) 966.
N.S. Hush, J. Chem. Phys. 28 (1958) 962.
W. Schmickler, J. Electroanal. Chem. 204 (1986) 31.
H. Gerischer, Z. Phys. Chem. NF 26 (1960) 223; 27 (1961) 40, 48.
W. Schmickler and J. Mohr, J. Chem. Phys. 117 (2002) 2867.
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Schmickler, W., Santos, E. (2010). Theoretical considerations of electron-transfer reactions. In: Interfacial Electrochemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-04937-8_10
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DOI: https://doi.org/10.1007/978-3-642-04937-8_10
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