Triplet Rydberg States of Aluminum Monofluoride.

Aluminum monofluoride (AlF) is a suitable molecule for laser cooling and trapping. Such experiments require 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 not been experimentally 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. 1988, 88, 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 determined the ionization potential of AlF to be 78,492(1) cm-1 by ionization from the d3Π state.

The chemistry of AlF and CaF production in buffer gas sources.

In this work, we explore the role of chemical reactions on the properties of buffer gas cooled molecular beams. In particular, we focus on scenarios relevant to the formation of AlF and CaF via chemical reactions between the Ca and Al atoms ablated from a solid target in an atmosphere of a fluorine-containing gas, in this case, SF6 and NF3. Reactions are studied following an ab initio molecular dynamics approach, and the results are rationalized following a tree-shaped reaction model based on Bayesian inference. We find that NF3 reacts more efficiently with hot metal atoms to form monofluoride molecules than SF6. In addition, when using NF3, the reaction products have lower kinetic energy, requiring fewer collisions to thermalize with the cryogenic helium. Furthermore, we find that the reaction probability for AlF formation is much higher than for CaF across a broad range of kinetic temperatures.

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 â† 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 â† X1Σ+ transition around 367 nm, which has a recoil limit in the µK 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 ← 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 ± 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.

Hyperfine-resolved optical spectroscopy of the A2Π â† X2Σ+ transition in MgF.

We report on hyperfine-resolved laser spectroscopy of the A2Π â† X2Σ+ transition of magnesium monofluoride (MgF), relevant for laser cooling. We recorded 25 rotational transitions with an absolute accuracy of better than 20 MHz, assigned 56 hyperfine lines, and determined precise rotational, fine, and hyperfine structure parameters for the A2Π state. The radiative lifetime of the A2Π state was determined to be 7.2(3) ns, in good agreement with ab initio calculations. The transition isotope shift between bosonic isotopologues of the molecule is recorded and compared to predicted values within the Born-Oppenheimer approximation. We measured the Stark effect of selected rotational lines of the A2Π â† X2Σ+ transition by applying electric fields of up to 10.6 kV cm-1 and determined the permanent electric dipole moments of 24MgF in its ground X2Σ+ and first excited A2Π states to be µX = 2.88(20) D and µA = 3.20(22) D, respectively. Based on these measurements, we caution for potential losses from the optical cycling transition due to electric field induced parity mixing in the excited state. In order to scatter 104 photons, the electric field must be controlled to below 1 V cm-1.