Electronic energy migration in solid versus liquid host matrices for concentrated perylenediimide dye solutions.

In this paper, we continue our evaluation of Forster-type theories of exciton diffusion in disordered environments. The perylenediimide dye Lumogen Red is used as a donor molecule in two different liquids, CHCl(3) and dimethylformamide, and the energy transfer to the acceptor molecule Rhodamine 700 is measured using time-resolved fluorescence decays. The exciton motion is measured over Lumogen Red concentrations ranging from 1 × 10(-4) to 5 × 10(-2) M, and the results are compared to previous results for exciton diffusion in a solid polymer. Depending on the theoretical approach used to analyze the data, we find that the energy migration in the liquids is a factor of 2-3 faster than in the solid polymer, even after taking molecular translation into account. Measurements for a Lumogen Red concentration of 10 mM in the different host environments yield diffusion constants ranging from 2.2 to 3.1 nm(2)/ns in the liquids, as compared to 1.1-1.2 nm(2)/ns in solid poly(methyl methacrylate) (PMMA). The results in the liquids are in good agreement with theoretical predictions and numerical simulations of previous workers, while the results in solid PMMA are 2-3 times slower. This discrepancy is discussed in the context of the rapid energetic averaging present in the liquid environments but absent in the solid matrix, where unfavorable configurations and low energy trapping sites are frozen in by the static disorder.