Single molecule probing of dynamics in supercooled polymers

Fluorescence experiments with single BODIPY molecules embedded in a poly(methyl acrylate) matrix have been performed at various temperatures in the supercooled regime. By using pulsed excitation, fluorescence lifetime and linear dichroism time trajectories were accessible at the same time. Both observables have been analyzed without data binning. While the linear dichroism solely reflects single particle dynamics, the fluorescence lifetime observable depends on the molecular environment, so that the dynamics from the polymer host surrounding a chromophore contributes to this quantity. We observe that the lifetime correlation decays slightly faster than polarization correlation, indicating the occurrence of large angular reorientations. Additionally, dichroism time trajectories have been adducted to reveal directly the geometry of rotational dynamics. We identify small but also significantly larger rotational jumps being responsible for the overall molecular reorientation.