Dye laser and thermal emission spectroscopy of the TbO molecule

Abstract

The rotational structure of six bands of the TbO molecule, including the 0–0 bands of electronic transitions III, IV, and V, was analyzed using laser excitation spectroscopy with selective fluorescence detection. From the fluorescence spectra obtained through excitation of selected rotational lines in these bands, the energies of 14 low-lying Ω states as well as ΔG1/2 values for the four lowest Ω states were determined. The values of Ω and rotational constants B and D were found for each, low-lying state and the upper states of the analyzed bands; an energy linkage for all the electronic transitions, whose rotational structure has been analyzed, is established. The ground state constants of TbO are (2σ—uncertainty in parentheses) Ω = 6.5, B0 = 0.3525(1) cm−1, D0 = 1.8(2) × 10−7 cm−1, ΔG1/2 = 837.1(1) cm−1, α = 1.5(1) × 10−3 cm−1.

Characterization of the Reaction Products of Laser-Ablated Late Lanthanide Metal Atoms with Molecular Oxygen: Infrared Spectra of LnO, LnO+, LnO-, LnO2, LnO2-, LnO3-, and (LnO)2 in Solid Argon

“…The neutral molecules agree with previous thermal matrix isolation and gas-phase assignments for the monoxides and one of the dioxides, − which confirms that these are monometal product species. Furthermore, variation of laser power over a 10-fold range retains the same sharp product bands for monometal species; weak, broad, unlisted bands in spectra of high laser power experiments could be due to unidentified metal cluster species.…”

“…The available experimental and theoretical literature pertaining to the lanthanide monoxide molecules is extensive. − Gas-phase assignments of the ground electronic states have been made for all of the neutral lanthanide monoxides except TmO, for which the vibrational frequency of the matrix-isolated species has been reported . There have also been identifications of several neutral lanthanide dioxides in rare gas matrices 13,14,16 and of dioxide cations in mass spectrometry observations. − Chemielectron spectroscopy has determined that most lanthanide monoxide cations and two dioxide cations form spontaneously upon reaction of atomic lanthanide metals with molecular oxygen …”

Laser Spectroscopy of Cerium Monofluoride: Ligand Field Assignments of Some 4f5d6p← 4f5d6sTransitions

“…Gaseous CeF was prepared in a high temperature tantalum tube furnace by resistively heating 0.2 g of Ce metal with 0.2 g of AlF 3 powder to 1900 K in a 9 mm diameter, 60 mm long Ta tube through which is passed an ac current of up to 150 A at 6 V. Descriptions of the experimental arrangement have been published previously (3,14,31). Gaseous CeF was prepared in a high temperature tantalum tube furnace by resistively heating 0.2 g of Ce metal with 0.2 g of AlF 3 powder to 1900 K in a 9 mm diameter, 60 mm long Ta tube through which is passed an ac current of up to 150 A at 6 V. Descriptions of the experimental arrangement have been published previously (3,14,31).…”

Strategies toward High-Temperature Lanthanide-Based Single-Molecule Magnets

“…It is important to mention that [LnO] −/0/+ are real existing units, with strong chemical bonds between the two atoms, as evidenced by very short equilibrium Ln–O distance obtained in calculations (Figure a) and derived from experiments (<1.8 Å). Such units were produced in the gas phase a long time ago and investigated by spectroscopic means. − We believe that deposition of these units into weakly bound hosts or nonconducting surfaces will not pose problems. In our opinion, the possible change in the oxidation state of the LnO unit, which might happen during such deposition, is unlikely to significantly affect the strong polarization of the orbital momentum on the Ln ion by the neighboring O atom.…”