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Optical absorption and emission measurements are reported for the Cs2NaSmCl6 and Cs2NaYCl6:Sm3+ (1 or 30 mol %) systems under variable-temperature (10–298 K) conditions. Twenty-six crystal-field levels spanning 13 multiplets of the Sm3+ 4f 5 electronic configuration are located and assigned on the basis of the experimental data, and these energy level results are rationalized in terms of a nine-parameter 4f-electron Hamiltonian. The most intense electric-dipole vibronic lines observed in the spectra are assigned to one-phonon vibronic transitions associated with the three odd-parity ‘‘moiety’’ modes of the SmCl3-6 octahedral clusters ν3(t1u), ν4(t1u), and ν6(t2u). Intensity calculations are reported for both the no-phonon magnetic-dipole (origin) transitions and the one-phonon (ν3, ν4, and ν6) electric-dipole vibronic transitions. [ABSTRACT FROM AUTHOR]

Optical absorption and emission measurements are reported for the Cs2NaYCl6:Nd3+ (∼5 mol %) system under variable-temperature (4.2–296 K) conditions. The absorption measurements span the 12 000–24 000 cm-1 spectral region, and emission spectra are presented throughout the 13 300–18 860 cm-1 region. All the spectra are consistent with the retention of octahedral (Oh) site symmetry for the Nd3+ ions down to 4.2 K. Thirty-four crystal-field levels spanning 14 multiplets of the Nd3+ 4f3 electronic configuration are located and assigned on the basis of the experimental data. The most intense lines observed in each of the multiplet-to-multiplet transition regions are assigned to one-phonon (electric-dipole) vibronic transitions associated with the three odd-parity moiety modes of the NdCl3-6 cluster, ν3(tlu), ν4(tlu), and ν6(t2u). The ν3 lines generally appear as doublets (split by ∼10–15 cm-1) and are displaced from magnetic-dipole origins by ∼245–260 cm-1; the ν4 lines are displaced from origins by ∼100 cm-1, and are generally sharp and symmetric; and the ν6 lines are generally asymmetric in shape (or appear as doublets split by ∼2–6 cm-1), and are displaced from origins by 70–75 cm-1. Additional vibronic lines are observed persistently at displacement energies of ∼40–45 and ∼55–60 cm-1, but these lines are considerably less intense than those assigned to the ν3, ν4, and ν6 moiety-mode vibrations. The energy level data obtained from experiment is rationalized in terms of a 9-parameter model which includes the radial spin-orbit interaction parameter (ζso), the Slater–Condon one-particle electrostatic interaction parameters (F2, F4, and F6), the two-particle electrostatic configuration-interaction parameters (α, β, and γ), and the octahedral (Oh) crystal-field interaction parameters... [ABSTRACT FROM AUTHOR]

Responds to a commentary about optical emission spectra and crystal-field analysis of thulium ion in cubic symmetry. Information on the emission excitation spectra obtained; Details of the energy levels of thulium chloride; Discussion on the crystal field parameters required to rationalize the available energy-level.