Ultrafast dynamics of the ns (n = 3,4) and 3d Rydberg states of O2.

The ultrafast dynamics of the lowest optically accessible Rydberg states of molecular oxygen (O2) has been studied by time resolved transient ionization. The process was triggered by the absorption of two pump photons in the 304 nm-220 nm range which corresponds to an energy range of 8.2 eV-11.3 eV, and probed by ionization with photons at 800 nm. From the analysis of the experimental data different time constants ranging from a few femtoseconds to hundreds of picoseconds were found. The identification of the states responsible for the measured lifetimes revealed important facts about the dynamics of the Rydberg states in this energy range, underlying the importance of the coupling between Rydberg and valence states in the relaxation mechanisms of the molecule.