Abstract
We report the first spectroscopic study of a complex consisting of a rare earth atom in combination with ammonia. Using two-color resonance-enhanced multiphoton ionization (REMPI) spectroscopy, the lowest energy electronic transition of YbNH(3) has been found in the near-infrared. The spectrum arises from a spin-forbidden transition between the (1)A(1) ground electronic state and the lowest (3)E excited electronic state. The transition is metal centered and approximately correlates with the Yb 6s6p (3)P ← 6s(2) (1)S transition. The observation of clear spin-orbit structure in the spectrum confirms the C(3v) symmetry of YbNH(3). Vibrational structure is also observed in the REMPI spectrum, which is dominated by excitation of the Yb-N stretching vibration.
Highlights
The physical and chemical properties of the rare earth element ytterbium (Yb) show many parallels to those of the alkaline earth elements
While its prime oxidation state is +3, Yb has a stable +2 oxidation state in many chemical compounds.1. This similarity with the alkaline earth metals derives from the filled and compact 4f sub-shell of Yb, which leaves it with a residual valence configuration of 6s2
When alkaline earth and rare earth metals dissolve in liquid ammonia they do not appear to produce solvated electrons, an observation that can be attributed to their higher ionization energies when compared to the alkali metals
Summary
The physical and chemical properties of the rare earth element ytterbium (Yb) show many parallels to those of the alkaline earth elements. Like the alkaline earths, as well as the alkali metals, Yb dissolves in liquid ammonia.. When alkaline earth and rare earth metals dissolve in liquid ammonia they do not appear to produce solvated electrons, an observation that can be attributed to their higher ionization energies when compared to the alkali metals. In our own laboratory we have exploited the photodepletion technique to obtain the first mid-IR spectra of Li(NH3)n and Na(NH3)n in the N–H stretching regions.11,12 These spectra have allowed a definitive identification of the first solvent shell closings. We present the findings from our first attempt to record gas phase spectra of a rare earth metal-ammonia complex, where the metal is Yb. We focus on the simplest species, YbNH3 and its deuterated analogue, YbND3. The spectrum obtained is assigned to a spin-forbidden metal-centered transition on the Yb atom
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