Strong-Coupling Modification of Singlet-Fission Dynamical Pathways

Abstract

We investigate theoretically the influence of strong lightmatter coupling on the initial steps of the phototriggered singlet-fission process. In particular we focus on intramolecular singlet fission in a TIPSpentacene dimer derivative described by a vibronic Hamiltonian including the optically active singlet excited states, doubly excited and charge transfer states, as well as the final triplet−triplet pair state. Quantum dynamics simulations of up to four dimers in the cavity indicate that the modified resonance condition imposed by the cavity strongly quenches the passage through the intermediate charge transfer and double-excitation states, thus largely reducing the triplet−triplet yield in the bare system. Subsequently, we modify the system parameters and construct a model Hamiltonian where the optically active singlet excitation lies below the final triplet−triplet state such that the yield of the bare system becomes insignificant. In this case we find that using the upper polariton as the doorway state for photoexcitation can lead to a much enhanced yield. This pathway is operative provided that the system is sufficiently rigid to prevent vibronic losses from the upper polariton to the dark-states manifold.