Singlet Fission in Lycopene H-Aggregates

Abstract

A theory of singlet fission (SF) in carotenoid dimers is applied to explain the SF in lycopene H-aggregates observed after high energy photoexcitation. The explanation proposed here is that a high energy, delocalized bright ${}^1{B}_u^{+}$ state first relaxes and localizes onto a single lycopene monomer. The high-energy intramonomer state then undergoes internal conversion to the $1^1{B}_u^{-}$ state. Once populated, the $1^1{B}_u^{-}$ state allows exothermic bimolecular singlet fission, while its internal conversion to the $2^1{A}_g^{-}$ state is symmetry forbidden. The simulation of SF predicts that the intramonomer triplet-pair state undergoes complete population transfer to the intermonomer singlet triplet-pair state within 100 ps. ZFS interactions then begin to partially populate the intermonomer quintet triplet-pair state up to ca. 2 ns, after which hyperfine interactions thermally equilibrate the triplet-pair states, thus forming free, single triplets within ca. 0.1 $\mu$s.