Triplet Rydberg states of aluminum monofluoride

Aluminum monofluoride (AlF) is a suitable molecule for laser cooling and trapping. Such experiments require an extensive spectroscopic characterization of the electronic structure. Two of the theoretically predicted higher lying triplet states of AlF, the counterparts of the well-characterized D¹Δ and E¹Π states, had experimentally not been identified yet. We here report on the characterization of the d³Π ($v=0-6$) and e³Δ ($v=0-2$) states, confirming the predicted energetic ordering of these states (J. Chem. Phys. 88 (1988) 5715-5725), as well as of the f³Σ⁺ ($v=0-2$) state. The transition intensity of the d³Π, v=3 $-$ a³Π, v=3 band is negligibly small. This band gets its weak, unexpected rotational structure via intensity borrowing from the nearby e³Δ, v=2 $-$ a³Π, v=3 band, made possible via spin-orbit and spin-rotation interaction between the d³Π and e³Δ states. This interaction affects the equilibrium rotational constants in both states; their deperturbed values yield equilibrium internuclear distances that are consistent with the observations. We determine the ionization potential of AlF to be 78492(1) cm⁻¹ by ionization from the d³Π state.