Empirical correlation found between the observed second-order rate constant,
,
for an intermolecular electron-transfer reaction
and the Gibbs energy of the photoinduced electron transfer process within
the encounter complex
(
):
with
and
the rate constant for the formation and separation, respectively, of the encounter
(precursor) complex,
,
the universal collision frequency factor,
the gas constant,
the absolute
temperature and
the activation Gibbs energy of the forward electron transfer reaction.
,
for an intermolecular electron-transfer reaction
and the Gibbs energy of the photoinduced electron transfer process within
the encounter complex
():
and
the rate constant for the formation and separation, respectively, of the encounter
(precursor) complex,
,
the universal collision frequency factor,
the gas constant,
the absolute
temperature and
the activation Gibbs energy of the forward electron transfer reaction.
Note:
In the original formulation of this equation the value
in acetonitrile was used.
in acetonitrile was used.
Source:
PAC, 2007, 79, 293
(Glossary of terms used in photochemistry, 3rd edition (IUPAC Recommendations 2006))
on page 413