Journal of Physical Chemistry A, Vol.104, No.24, 5825-5836, 2000
Electronic energy transfer in multichromophoric arrays. The effects of disorder on superexchange coupling and energy transfer rate
The effects of diagonal (site energy) and off-diagonal (intermolecular interaction) disorder arising from the distribution of ionization energies on superexchange coupling and the corresponding electronic energy transfer (EET) rate are considered. The effective donor-acceptor coupling is obtained using the Dyson's equations-based solution of the Green's function for both the orthogonal and nonorthogonal basis sets. In a disordered multichromophoric array, the effective superexchange coupling is shown to be enhanced. Furthermore, the competing roles of the multiple pathways when next-to-nearest-neighbor interactions exist behave differently depending on the type and extent of disorder. It is demonstrated that the exponential falloff of the energy transfer rate with increasing donor-acceptor distance weakens when disorder is present. Moreover, this exponential decay is more apparent when the donor-bridge energy gap is reduced. A method to treat EET at the molecular orbital level using Dyson's equations is also presented when the coupling between adjacent bridge sites is either Dexter or through-configuration interaction. We find that the superexchange coupling derived from the through-configuration interaction is the dominant mode of superexchange EET. The implications of the results for the design of molecular arrays with optimized energy transfer properties are considered.