Spin-dependent recombination mechanisms for quintet biexcitons generated through singlet fission

We investigate the physical mechanisms for spin-dependent recombination of a strongly bound pair of triplet excitons generated by singlet fission and forming a spin quintet (total spin of two) biexciton. For triplet excitons the spin-dependent recombination pathways can involve intersystem crossing or triplet-triplet annihilation back to the singlet ground state. However, the modeling of spin-dependent recombination for quintets is still an open question. Here we introduce two theoretical models and compare their predictions with the broadband optically detected magnetic-resonance spectrum of a long-lived quintet biexciton with known molecular structure. This spectrum measures the change in the fluorescence signal induced by microwave excitation of each of the ten possible spin transitions within the quintet manifold as a function of a magnetic field. While most of the experimental features can be reproduced for both models, the behavior of some of the transitions is only consistent with the quintet spin-recombination model inspired by triplet intersystem crossing which can reproduce accurately the experimental two-dimensional spectrum with a small number of kinetic parameters. Thus quantitative analysis of the broadband optically detected magnetic-resonance signal enables quantitative understanding of the dominant spin-recombination processes and estimation of the out-of-equilibrium spin populations.