Triplet excitation transfer in glassy systems: Spatial and spectral diffusion

Abstract

Triplet excitation transfer among benzophenone molecules dissolved in glassy 2-methyltetrahydrofuran is studied by recording the emission and the optical depolarization as a function of wavelength and time. The transport mechanism is based upon exchange interaction and subject to the random character of both jump distances and site energies. Optical anisotropy data are used to gauge the probability of an excitation to remain on its original site. The anisotropy is observed to decrease by a factor of 2 from high to low energies within the inhomogeneously broadened emission band, clearly indicating hopping-mediated thermalization within the density of states. Within their excited-state lifetime the excitons do not reach the steady-state energies, but solvation allows the observation of that energy level. Unexpectedly, we find that the transfers at very short times do not contribute as much to spectral diffusion as the subsequent transport. Because the short-time hops target sites as close as approximately 1 nm, this observation suggests spatially correlated site energies for these short distances.