Singlet-Fission-Induced Enhancement of Third-Order Nonlinear Optical Properties of Pentacene Dimers

[Image: see text] Using quantum chemical calculations and exciton dynamics simulations, we investigate the static second hyperpolarizability γ [the third-order nonlinear optical (NLO) property at the molecular scale] of slip-stacked pentacene dimer models in the correlated-triplet-pair [(1)(TT)] state created from the singlet excited state in the singlet fission (SF) process. It is found that the SF induces significant (∼20 times at maximum) enhancement of γ/monomer in the (1)(TT) state as compared to that in the singlet ground state. The origin of the remarkable enhancement of γ/monomer is revealed by analyzing the γ density distribution and the intermolecular orbital interaction. Furthermore, we clarify molecular packings suitable for highly efficient SF and largely enhanced γ values of a novel class of SF-induced NLO systems, which have promising potential to surpass the conventional NLO systems.