Excitonic intraband relaxation and polarization anisotropies in PTCDA on femtosecond and picosecond timescales

We report on investigations of optical excitations in polycrystalline organic molecular crystals with quasi-1D-stacked crystal structure and negative exciton dispersion. As model system, we choose thin films of the perylene derivative 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). Using pump–probe spectroscopy, we show how the relaxation from the absorbing state towards the border of the Brillouin zone occurs on a 120 fs timescale. Time-resolved luminescence anisotropy gives evidence that as a result of the coherent coupling between adjacent stacks, populations of the Davydov-split states that are prepared during photo-excitation relax into the emitting states in less than 5 ps. The behavior of the luminescence anisotropy can be explained by the orientation of the two PTCDA molecules in the unit cell. However, a full understanding of the ultrafast pump–probe anisotropy requires novel explanations beyond current models.