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inverted region (for electron transfer)

In plots relating rate constants to charges in standard Gibbs energy (Δ G °) for electron transfer a region may occur in which the rate constants decrease as the exergonicity of the reaction increases. This region is often referred to as the inverted region and its presence is predicted by the theory developed for outer sphere electron transfer for the case − Δ G ° > λ in the Marcus equation, λ being the reorganization energy. Note the similarity to the energy gap law for radiationless conversion of an excited state.
Source:
PAC, 1996, 68, 2223 (Glossary of terms used in photochemistry (IUPAC Recommendations 1996)) on page 2249
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IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.
Last update: 2014-02-24; version: 2.3.3.
DOI of this term: doi:10.1351/goldbook.I03152.
Original PDF version: http://www.iupac.org/goldbook/I03152.pdf. The PDF version is out of date and is provided for reference purposes only. For some entries, the PDF version may be unavailable.
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