Formation Pathways of the Spin-Correlated, Spatially Separated $^{1}$(T...T) State in the Singlet Fission Process of Perylene Diimide Stacks

Abstract: For the theoretical screening of Singlet Fission (SF) rates in molecular aggregates, commonly dimer model systems are employed. However, there is experimental evidence, that the SF process proceeds from the $^{1}$(TT) state via an triplet-triplet energy transfer process to a further intermediate: a $^{1}$(T...T) state with two non-adjacent, spin-correlated triplets, which cannot be captured by the dimer models. In this work, we extend Michl's diabatic frontier orbital model to trimer systems, for which we automatically generate the diabatic two and three-center couplings using symbolic algebra. We apply this method to study the packing dependence of the $^{1}$(T...T) formation in the perylene diimide (PDI) trimer stack. We find that efficient triplet-triplet energy transfer is facilitated by structural motifs for which also significant excimer character can be observed. Furthermore, the coupling shows a local maximum for the structural motif that has been assigned to efficient $^{1}$(TT) population. Employing second order perturbation theory, we study the interference of the individual electronic pathways that arise in the PDI trimer system, allowing us to reproduce the packing dependence of the SF rates derived from the Redfield simulations in the work by Mirjani et. al. (Phys. Chem. C 2014, 118, 26, 14192-14199).