https://doi.org/10.1140/epjd/e2003-00222-6
On the theory of nonadiabatic bridge–mediated electron transfer
Influence of structural and energetic disorder
1
Institut für Physik,
Humboldt–Universität zu Berlin, Hausvogteiplatz 5-7,
10117 Berlin, Germany
2
Bogolyubov Institute for Theoretical Physics, Ukr. Natl.
Acad. Sci., 14-b Metrologichna str., 03143 Kiev, Ukraine
Corresponding author: a may@physik.hu-berlin.de
Received:
11
February
2003
Revised:
14
April
2003
Published online:
22
July
2003
Effects of structural and energetic disorder on nonadiabatic electron transfer (ET) reactions are discussed theoretically. To account for the sequential as well as the superexchange mechanism of ET our recent approach is used presented in J. Phys. Chem. A 105, 10176 (2001). The overall charge motion is characterized by the numerical solution of rate equations for the electronic state populations and an averaging with respect to the disorder configurations. Introducing a single effective transfer rate which can be deduced from the experiment the dependence of this rate is discussed on the geometry of the ET system as well as on the disorder model. The theory is applied to donor–acceptor complexes connected by oligomers of the amino acid proline. In particular, a pronounced dependence is found of the effective transfer rate on disorder with respect to the reorganization energy.
PACS: 34.10.+x – General theories and models of atomic and molecular collisions and interactions (including statistical theories, transition state, stochastic and trajectory models, etc.) / 34.30.+h – Intramolecular energy transfer; intramolecular dynamics; dynamics of van der Waals molecules / 31.70.Hq – Time-dependent phenomena: excitation and relaxation processes, and reaction rates
© EDP Sciences, Società Italiana di Fisica, Springer-Verlag, 2003
