Enhancing Singlet Fission Dynamics by Suppressing Destructive Interference between Charge-Transfer Pathways.

We apply a real-time path-integral approach to investigate the charge-transfer (CT)-mediated singlet fission quantum dynamics in a model pentacene dimer. Our path-integral method gives reliable fission dynamics across various reaction regimes as well as a broad range of reorganization energies and temperatures. With this method, we investigated the destructive interference between the two CT-mediated fission pathways and discovered two mechanisms that can suppress this deleterious effect. First, increasing the energy gap between the two CT states effectively shuts down the high-lying CT pathway, leaving a better functioning low-lying CT pathway with a minimum amount of destructive interference. Second, intermolecular vibrations induce electronic coupling fluctuations, such that the destructive cancellations due to the different signs in static electronic couplings are suppressed. Our numerical results suggest that these two effects can enhance the fission rate up to three times. These findings reveal promising design principles for more efficient singlet fission materials.