Relationship between the barrier
to thermal electron transfer
, the energy of a corresponding optical charge-transfer transition(),
and the overall change in standard Gibbs energy accompanying thermal electron transfer().
Assuming a quadratic relation between the energy of the system and its distortions
from equilibrium (harmonic oscillator model) the expression obtained is:
The simplest form of this expression obtains for degenerate electron transfer()
in e.g. symmetrical mixed valence
Note that for this situation the Marcus equation
PAC, 1996, 68, 2223
(Glossary of terms used in photochemistry (IUPAC Recommendations 1996))
on page 2253
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