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The High-Resolution 4f-5d Absorption Spectrum of Divalent Dysprosium (Dy 2+ ) in Strontium Chloride Host SrCl 2 : Fine Structure and Zero-Phonon Transitions Revealed

The High-Resolution 4f-5d Absorption Spectrum of Divalent Dysprosium (Dy 2+ ) in Strontium Chloride Host SrCl 2 : Fine Structure and Zero-Phonon Transitions Revealed

Journal of Physical Chemistry. a 122(4): 923-928

The virtual lack of information on electronic spectra of divalent lanthanide elements (Ln2+) other than Sm2+, Eu2+, Tm2+, and Yb2+ has prompted us to set for synthesis and characterization of novel Ln2+ systems. First successful attempt concerned SrCl2/Nd2+ single crystals. Here, we report stabilization of divalent dysprosium in a chloride host. Importantly this has been accomplished with Dy ions introduced in a divalent state during synthesis, unlike by γ-irradiation of Dy3+ systems employed previously. This synthesis method yields good quality SrCl2/Dy2+ single crystals. The electronic absorption spectra of Dy2+ doped in SrCl2 have been recorded with high resolution at liquid helium temperature (4.2 K). Identification of the absorption bands occurring in the spectral range of 5000-45000 cm-1 is achieved. On the basis of theoretical calculations using semiempirical Hamiltonian model, assignment of bands and determination of the Hamiltonian parameters for Dy2+(4f95d1) configuration is carried out. The experimental and theoretical studies reveal fine structure and zero-phonon transitions and thus enable high-resolution assignment of spectral lines. It is shown that spin-forbidden transitions gain relatively high intensity due to significant admixing of low-spin character to nominally high-spin states.

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Accession: 065587854

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PMID: 29304287

DOI: 10.1021/acs.jpca.7b08620

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