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• W2099420904 abstract "The emission spectra of microcrystalline Cs2NaTbCl6 and Cs2Na(Y0.99Tb0.01)Cl6 have been measured at room temperature and at 77 K. The crystal structures of these compounds are face-centered cubic and the terbium (III) ions lie at sites of octahedral (Oh) symmetry surrounded by six chloride ions. Emission is observed from both the 5D3 and 5D4 excited states of Tb3+. Assignments have been made for nearly all of the magnetic-dipole transitions split out of the Tb3+ 7F6, 7F5, 7F4, 7F3, 7F2, 7F1 ← 5D4 and 7F4, 7F2 ← 5D3 transitions. These assignments are based on the calculated transition energies and relative magnetic-dipole strengths and intensities obtained from a weak-field crystal-field analysis of octahedral TbCl63− units. Magnetic-dipole lines dominate the spectra for transitions of ΔJ = ±1 free-ion parentage, whereas both magnetic-dipole lines and vibronically induced electric-dipole lines contribute significantly to the emission intensities of the ΔJ = 0, ±2 transitions. The crystal-field sub-levels of both 5D3 and 5D4 appear to reach a Boltzmann thermal equilibrium prior to emission. Emission from 5D3 is partially quenched in going from low temperature to high temperature and in going from Cs2NaYCl6: Tb3+ (1%) to Cs2NaTbCl6. This study has led to the identification and assignment of nearly all of the pure magnetic-dipole transitions split out of the Tb3+ 7F6, 7F5, 7F4, 7F3, 7F2, 7F1 ← 5D4 and 7F4, 7F2 ← 5D3 transitions in crystal-line Cs2NaTbCl6. The assignments were based on calculated transition energies and relative magnetic-dipole strengths (and intensities) obtained from a (weak-field) crystal-field analysis of octahedral (Oh) TbCl63− clusters. Excellent agreement between the calculated and observed relative intensities of the magnetic-dipole lines was achieved by assuming a Boltzmann equilibrated set of crystal-field sub-levels for both the 5D4 and 5D3 emitting states. Furthermore, the experimental results suggest that 5D4 ← 5D3 relaxation is temperature-dependent. The energy levels calculated and displayed in table 1 appear to be qualitatively correct and are in semiquantitative agreement with the emission results (as interpreted in section 4). Calculated and observed transition energies for the assigned magnetic-dipole transitions generally agree to within 0.2%. One of the most remarkable features of the emission spectra obtained on Cs2NaTbCl6 is the absence of any vibrational structure in the ΔJ = ± 1 transitions (7F6, 7F3 ← 5D4 and 7F4, 7F2 ← 5D3), and the presence of extensive vibrational structure in the ΔJ = O, ±2 transitions (7F6, 7F4, 7F2 ← 5D4). If other than OO vibronic transitions do contribute to the ΔJ = ±1 emissions, their intensities must be at least two or three orders-of-magnitude weaker than the OO magnetic-dipole lines. Vibronically induced electric-dipole transitions appear, however, to make substantial contributions to the 7F6, 7F4, 7F2 ← 5D4 emission spectra. A clear-cut theoretical explanation for the absence of vibrational structure in the ΔJ = ±1 transitions is not readily apparent. We are presently examining this problem in greater detail." @default.
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• W2099420904 date "1977-12-01" @default.
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• W2099420904 title "Emission spectra of Cs2NaTbCl6 and Cs2NaYCl6: Tb3+" @default.
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• W2099420904 doi "https://doi.org/10.1016/0301-0104(77)85163-x" @default.
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