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 systems:
Note that for this situation the
Marcus equation reads:
Source:
PAC, 1996, 68, 2223
(Glossary of terms used in photochemistry (IUPAC Recommendations 1996))
on page 2253
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.
