Femtosecond excitation tuning and site energy memory of population transfer in poly(<i>p</i>-phenylenevinylene): Gated luminescence experiments and simulation

Abstract

We present a comprehensive experimental and computational study on fs-relaxational dynamics of optical excitations in the conjugated polymer poly(p-phenylenevinylene) (PPV) under selective excitation tuning conditions into the long-wavelength, low-vibrational S1ν=0-density-of-states (DOS). The dependence of single-wavelength luminescence kinetics and time-windowed spectral transients on distinct, initial excitation boundaries at 1.4 K and at room temperature was measured applying the luminescence up-conversion technique. The typical energy-dispersive intra-DOS energy transfer was simulated by a combination of static Monte Carlo method with a dynamical algorithm for solving the energy-space transport Master-Equation in population-space. For various, selective excitations that give rise to specific S1-population distributions in distinct spatial and energetic subspaces inside the DOS, simulations confirm the experimental results and show that the subsequent, energy-dissipative, multilevel relaxation is hierarchically constrained, and reveals a pronounced site-energy memory effect with a migration-threshold, characteristic of the (dressed) excitation dynamics in the disordered PPV many-body system.