RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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 â 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.
RESUMEN
Clusters of para-hydrogen (pH2) and ortho-deuterium (oD2) have been assembled around an OCS chromophore molecule inside He droplets in a molecular beam and studied via IR diode laser depletion spectroscopy (nu approximately 2060 cm-1). The superfluid 4He droplets provide a gentle host ensuring a constant low temperature of either T = 0.38 K for 4He droplets or T = 0.15 K for both the pure 3He and mixed 4He-3He droplets. The spectra show well resolved rotational structure of the vibrational bands for each attached hydrogen molecule in the range n = 1-8. With only one (n = 1) attached pH2, HD or an oD2 molecule the best fit rotational constants were used to determine the structure of the complex, which was found to be in surprisingly good agreement with quantum chemical calculations for the free complex. With n = 5 and 6 the Q-branch disappears for the pH2 clusters but not for the oD2 clusters which is consistent with a donut model. The moments of inertia of the pH2 and the oD2 complexes are explained by a new model in which each of the 18 attached helium atoms in a shell surrounding the OCS molecule are assigned a mass of 0.55, while each attached H2 and D2 molecule has an effective mass of about 10 and 12 u, respectively.