Spectroscopic characterization of singlet-triplet doorway states of aluminum monofluoride

Aluminum monofluoride (AlF) possesses highly favorable properties for laser cooling, both via the A1Π and a3Π states. Determining efficient pathways between the singlet and the triplet manifold of electronic states will be advantageous for future experiments at ultralow temperatures. The lowest rotational levels of the A1Π, v = 6 and b3Σ+, v = 5 states of AlF are nearly iso-energetic and interact via spin–orbit coupling. These levels thus have a strongly mixed spin-character and provide a singlet–triplet doorway. We here present a hyperfine resolved spectroscopic study of the A1Π , v = 6//b3Σ+, v = 5 perturbed system in a jet-cooled, pulsed molecular beam. From a fit to the observed energies of the hyperfine levels, the fine and hyperfine structure parameters of the coupled states and their relative energies as well as the spin–orbit interaction parameter are determined. The standard deviation of the fit is about 15 MHz. We experimentally determine the radiative lifetimes of selected hyperfine levels by time-delayed ionization, Lamb dip spectroscopy, and accurate measurements of the transition lineshapes. The measured lifetimes range between 2 and 200 ns, determined by the degree of singlet–triplet mixing for each level