A multistep kinetic model in which solvent motion is
treated in
the framework of Marcus theory and the rates of the elementary electron
transfer step are evaluated at full quantum mechanical level is proposed
and applied to the calculation of the rates of intramolecular electron
transfer reactions in rigidly spaced D–Br–A (D = 1,1′-biphenyl
radical anion, Br = androstane) compounds, for five acceptors (A)
in three organic solvents with different polarity. The calculated
rates agree well with experimental ones, and their temperature dependence
is almost quantitatively reproduced.
Using a very recently proposed theoretical model, electron transfer rates in solution are calculated from first principles for different donor-acceptor pairs in tetrahydrofuran. We show that this approach, which integrates tunneling effects into a classical treatment of solvent motion, is able to provide reliable rate constants and their temperature dependence, even in the case of highly exergonic reactions, where Marcus’ theory usually fails.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.