Does Förster Theory Predict the Rate of Electronic Energy Transfer for a Model Dyad at Low Temperature?

The use of the Förster model to predict the dynamics of resonant electronic energy transfer (RET) in a model donor−acceptor dyad (a terphenyl-bridged perylene diimide (PDI)−terrylene diimide (TDI) dyad molecule) embedded at low temperature in a PMMA matrix is tested against experiment. The relevant ingredients involved in the Förster rate for RET, namely electronic coupling, spectral overlap, and screening effects, are accounted for in a quantitative manner. Electronic couplings are obtained from time-dependent density functional theory calculations, and the effect of the PMMA environment is included both on the transition densities and on their interaction through the IEFPCM model. We find that the presence of the terphenyl bridge induces a slight delocalization of the PDI and TDI transition densities over the bridge originating in a 56% increase in the coupling and in the breakdown of the dipole−dipole approximation. The spectral overlap is determined on the basis of a detailed simulation of the homogeneously broadened donor emission and acceptor absorption line shapes determined by fitting the single molecule spectra measured at 1.2 K. The corresponding distribution of spectral overlap throughout the ensemble is then estimated by assuming an uncorrelated inhomogeneous line broadening for the donor and acceptor. Combining the calculated electronic couplings and spectral overlaps sampled from Monte Carlo realizations of the energetic disorder, we obtain a mean RET time (8 ps) and a distribution in reasonable agreement with experiment.