Quantum Dynamics of Electron–Hole Separation in Stacked Perylene Diimide-Based Self-Assembled Nanostructures

We report on high-dimensional quantum dynamical simulations of electron–hole separation in self-assembled mesomorphic nanostructures composed donor–acceptor conjugated co-oligomers. The latter are based perylene diimide (PDI) acceptor units combined with fluorene-thiophene-benzothiadiazole donor units, which form highly ordered, stacked structural motifs upon self-assembly. Simulations shown for a first-principles parametrized model lattice 25 PDI under the effects an applied external field and temperature. carried out multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method nearly 900 vibrational degrees freedom electronic states. Temperature included using thermofield dynamics approach. A transition between short-time coherent kinetic regime is highlighted. From flux-over-population analysis, dissociation rates obtained range 5–20 ns–1 absence static disorder, exhibiting moderate temperature dependence. These results can be employed as benchmark to calibrate parametrization Monte Carlo much larger sizes.