Triplet Separation after the Fastest Intramolecular Singlet Fission in the Smallest Chromophore

Singlet fission is of key importance in harvesting solar energy in solar cells, as it generates a pair of triplet excitons on the incidence of a photon. This phenomenon is not yet widely employed in the organic photovoltaics industry mostly because of the rarity of singlet fission chromophores. Pyrazino[2,3-g]quinoxaline-1,4,6,9-tetraoxide was recently designed as the smallest intramolecular singlet fission chromophore, and it undergoes the fastest singlet fission with a 16 fs time scale. The subsequent separation of the generated triplet-pair is of likewise importance as their efficient generation. Through quantum chemistry calculations and quantum dynamics simulations, we show that the triplet-pair separates to residing on two chromophores with an ∼80% probability on each collision between a chromophore with the triplet-pair and a ground state chromophore. Avoided crossing, instead of conical intersection, is involved in the efficient exciton separation.