Conformational Dynamics Guides Coherent Exciton Migration in Conjugated Polymer Materials: First-Principles Quantum Dynamical Study.

We report on high-dimensional quantum dynamical simulations of photoinduced exciton migration in a single-chain oligothiophene segment, in view of elucidating the controversial nature of the elementary exciton transport steps in semiconducting polymers. A novel first-principles parametrized Frenkel J aggregate Hamiltonian is employed that goes significantly beyond the standard Frenkel-Holstein Hamiltonian. Departing from a nonequilibrium state created by photoexcitation, these simulations provide evidence of an ultrafast two-timescale process at low temperatures, involving exciton-polaron formation within tens of femtoseconds (fs), followed by torsional relaxation on an ∼400  fs timescale. The second step is the driving force for exciton migration, as initial conjugation breaks are removed by dynamical planarization. The quantum coherent nature of the elementary exciton migration step is consistent with experimental observations highlighting the correlated and vibrationally coherent nature of the dynamics on ultrafast timescales.