Ultrafast electronic relaxations from the S₃ state of pyrene

The ultrafast relaxation occurring in pyrene upon excitation at 4.68 eV was studied in a supersonic gas-jet fs pump-probe experiment. Mass spectrometry and velocity map imaging of photoelectrons produced by probing via multiphoton ionisation at 800 nm reveal that the initially prepared wave packet exhibits a fast relaxation (<80 fs), followed by a slower one of 200 fs. By comparing the propensity rules of photoionisation observed at one color with ab initio calculations, we tentatively assign these two timescales to a first internal conversion to the dark bB3g state followed by a second one to the long lived aB2u first excited state. Vertical excitation energies determined using ab initio Multi-State Complete Active Space 2nd order Perturbation Theory (MS-CASPT2), as well as oscillator strengths between several electronic states, are reported.