A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers
Cornell University Ithaca United States
Pagination or Media Count:
Interest in materials that undergo singlet fission SF has been catalyzed by the potential to exceed the ShockleyQueisser limit of solar power conversion efficiency. In conventional materials, the mechanism of SF is an intermolecular process xSF, which is mediated by charge transfer CT states and depends sensitively on crystal packing or molecular collisions. In contrast, recently reported covalently coupled pentacenes yield 2 triplets per photon absorbed in individual molecules the hallmark of intramolecular singlet fission iSF. However, the mechanism of iSF is unclear. Here, using multireference electronic structure calculations and transient absorption spectroscopy, we establish that iSF can occur via a direct coupling mechanism that is independent of CT states. We show that a near-degeneracy in electronic state energies induced by vibronic coupling to intramolecular modes of the covalent dimer allows for strong mixing between the correlated triplet pair state and the local excitonic state, despite weak direct coupling.