Spectroscopic characterization of the a³Π state of aluminum monofluoride

Spectroscopic studies of aluminum monofluoride (AlF) have revealed its highly favorable properties for direct laser cooling. All Q lines of the strong A¹Π leftarrow X¹Σ^+ transition around 227 nm are rotationally closed and thereby suitable for the main cooling cycle. The same holds for the narrow, spin-forbidden a³Π leftarrow X¹Σ^+ transition around 367 nm which has a recoil limit in the micro Kelvin range. We here report on the spectroscopic characterization of the lowest rotational levels in the a³Π state of AlF for v=0-8 using a jet-cooled, pulsed molecular beam. An accidental AC Stark shift is observed on the a³Π₀, v=4 leftarrow X¹Σ^+, v=4 band. By using time-delayed ionization for state-selective detection of the molecules in the metastable a³Π state at different points along the molecular beam, the radiative lifetime of the a³Π₁, v=0, J=1 level is experimentally determined as τ=1.89 pm 0.15 ms. A laser/radio-frequency multiple resonance ionization scheme is employed to determine the hyperfine splittings in the a³Π₁, v=5 level. The experimentally derived hyperfine parameters are compared to the outcome of quantum chemistry calculations. A spectral line with a width of 1.27 kHz is recorded between hyperfine levels in the a³Π, v=0 state. These measurements benchmark the electronic potential of the a³Π state and yield accurate values for the photon scattering rate and for the elements of the Franck-Condon matrix of the a³Π - X¹Σ^+ system.