Intermolecular
Vibrational Modes Speed Up Singlet
Fission in Perylenediimide Crystals
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Abstract
We report numerical simulations based
on a non-Markovian density
matrix propagation scheme of singlet fission (SF) in molecular crystals.
Ab initio electronic structure calculations were used to parametrize
the exciton and phonon Hamiltonian as well as the interactions between
the exciton and the intramolecular and intermolecular vibrational
modes. We demonstrate that the interactions of the exciton with intermolecular
vibrational modes are highly sensitive to the stacking geometry of
the crystal and can, in certain cases, significantly accelerate SF.
This result may help in understanding the fast SF experimentally observed
in a broad range of molecular crystals and offers a new direction
for the engineering of efficient SF sensitizers