Quantum Interference in Singlet Fission: J- and H-Aggregate Behavior.

Abstract

The quantum interference in singlet fission (SF) among the multiple pathways from singlet excited states to correlated triplet pair states is comprehensively investigated. The analytical analysis reveals that this interference is strongly affected by the exciton-exciton coupling and is closely related to the property of J- and H-type of aggregates. Different from the interference in the spectra of aggregates, which depends only on the sign of exciton-exciton coupling, the interference in SF is additionally related to the signs of couplings between singlet excited states and triplet pair states. The interference dynamics is further demonstrated numerically by a time-dependent wavepacket diffusion method with electron-phonon interactions incorporated. Finally, we take a pentacene dimer as a concrete example to show how to adjust the constructive and destructive interferences in SF dynamics in terms of J-/H-aggregate behaviors. The results presented here may provide guiding principles for designing efficient SF materials through directly tuning quantum interference via morphology engineering.