Rehm–Weller equation

Empirical correlation found between the observed second-order rate constant, $k q$ , for an intermolecular electron-transfer reaction and the Gibbs energy of the photoinduced electron transfer process within the encounter complex ( $Δ ET G o$ ):

$k q = k d 1 + k d K d Z exp ( Δ G ‡ R T ) + exp ( Δ ET G o R T )$

with $k d$ and $k −d$ the rate constant for the formation and separation, respectively, of the encounter (precursor) complex, $K d = k d k −d$ , $Z$ the universal collision frequency factor, $R$ the gas constant, $T$ the absolute temperature and $Δ G ‡$ the activation Gibbs energy of the forward electron transfer reaction.

Note:

In the original formulation of this equation the value $k d K d Z = 0.25$ in acetonitrile was used.

Source:

PAC, 2007, 79, 293 (Glossary of terms used in photochemistry, 3rd edition (IUPAC Recommendations 2006)) on page 413

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Cite as:
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. https://doi.org/10.1351/goldbook.

Last update: 2014-02-24; version: 2.3.3.

DOI of this term: https://doi.org/10.1351/goldbook.RT07472.

Original PDF version: http://www.iupac.org/goldbook/RT07472.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 The PDF version is out of date and is provided for reference purposes only.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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