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Abstract

The importance of singlet fission as a fundamental process with a variety of implications in energy harvesting cannot be overstated. The challenge is in characterizing the energy states of these large singlet fission molecular aggregates that participate in the process. Large dimensionality and essential multi-configuration nature of the electronic states of interest combine to make accurate ab initio calculations prohibitively difficult. We present a spin-resolved tight-binding excitonic model for singlet fission that can be parameterized based on ab initio calculations on monomers and dimers of molecules, and is highly suitable for the study of aggregates using tensor network methods such as the density matrix renormalization group. This tensor network coarse-grained model is demonstrated specifically on the pentacene crystal, where we evaluate the spectra and density of states. We show the natural emergence of bands of states in some cases, and characterize them. Through an analysis of entanglement entropy of the eigenstates, we gain crucial insight into the extent of their multireference character. This method is useful in understanding not just the structure of these extended aggregates, but also being the cornerstone for incorporation of vibronic features and simulation of the singlet fission dynamics.