Systems containing divalent lanthanide elements (Ln2+) are hard to synthesize and thus their characterization is still largely an unexplored area. The absorption spectra of most divalent Ln2+ ions were, until recently, obtained nearly exclusively for Ln2+:CaF2 crystals. In the first paper in a series devoted to systematic analysis of f-d absorption spectra of Ln2+ in alkali-halides hosts we presented new experimental data for Nd2+ and Dy2+ ions in SrCl2 and reanalyzed available data for SrCl2: Ln2+ (Ln = Sm, Eu, Tm, and Yb). The increased number of spectral data on the f-d transitions for Ln2+ ions makes SrCl2 the second best studied matrix. The second paper in this series is devoted to CaCl2:Ln2+ (Ln = Sm, Eu, Tm, and Yb). The first absorption, emission, and excitation spectra for Sm2+, Eu2+ and Yb2+ in CaCl2 are reported. Using a uniform methodology based on a parametric Hamiltonian model proposed in Part I, a systematic analysis of the spectra is performed. This approach yields refined and consistent sets of the free-ion parameters and crystal-field (CF) ones. Systematic CF analysis of the large spectral dataset for CaCl2:Ln2+ consisting of a total of four ions allows revealing inherent trends across the Ln series. Our results enable partial verification of the trends uncovered in Part I for Ln2+:SrF2. It appears that the trends in the free-ion parameters and, to a lesser extent, CF ones observed for one Ln2+ ion are sufficiently systematic to allow for tentative predictions of the spectrum for any lanthanide ion based on the sets of parameters derived from the spectra obtained for another ion in the same matrix.
Journal of Luminescence – Elsevier
Published: May 1, 2018
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