Singlet fission, a multistep molecular process in which one photon generates two triplet excitons, holds great technological promise. Here, by applying a combination of transient transmittance and two-dimensional electronic spectroscopy with 5 fs laser pulses, we resolve the full set of fission steps before the onset of spin dephasing. In addition to its role as a viable singlet fission material, single-crystalline rubrene is selected because its energetics and transition dipole alignment uniquely allow for the unambiguous identification of the various fission steps through their contributions to distinct spectroscopic features. The measurements reveal that the neighboring correlated triplet pair achieves its maximum population within 20 fs. Subsequent growth of the triplet signal on picosecond time scales is attributable to spatial separation of the triplets, proceeding nonadiabatically through weakly coupled but near-resonant states. As such, we provide evidence in crystalline rubrene for a singlet fission step that, until now, has not been convincingly observed.
