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Influence of the chemical environment on the electronic structure and spectroscopic properties of Er3+ doped Cs3Lu2Cl9, Cs3Lu2Br9, and Cs3Y2I9

Authors :
Markus P. Hehlen
Hans U. Güdel
Stefan R. Lüthi
Source :
The Journal of Chemical Physics. 110:12033-12043
Publication Year :
1999
Publisher :
AIP Publishing, 1999.

Abstract

Energies and intensities of 114, 101, and 76 f–f absorption transitions of Er3+ are determined by high-resolution spectroscopy in the closely related host lattices Cs3Lu2Cl9, Cs3Lu2Br9, and Cs3Y2I9, respectively. The observed trends in the energy-level structure reflect the increasing covalency and the length of the Er3+–X− bond. The decreasing Coulomb repulsion of the 4f electrons, spin–orbit coupling, and crystal-field potential reduces the energy splittings of the SL, SLJ, and SLJMJ states by 0.5%, 0.5%, and 25%, respectively, along the series Cl–Br–I. Energy-level calculations that include crystal-field and correlation crystal-field terms in the effective Hamiltonian, reproduce most of the experimentally found trends. Root-mean-square standard deviations of 18.0, 19.2, and 21.9 cm−1 are reached in least-squares fits to the experimental crystal-field energies. The f–f transition intensities increase along the series Cl–Br–I as a result of the decreasing energy of the f–d bands. In the iodide compound, where the first f–d bands are as low as 30 000 cm−1, this influence is especially pronounced for the f–f absorptions at higher energy. The quality of the wavefunctions obtained in the energy-level calculations is not sufficient to reliably calculate the relative absorption intensities of individual crystal-field components within a given multiplet transition. This deficiency is ascribed to small deviations of the actual coordination geometry of Er3+ from the C3v point group symmetry that was assumed in the calculation. Intensities are analyzed on the level of multiplet-to-multiplet transitions using the Judd–Ofelt formalism.

Details

ISSN :
10897690 and 00219606
Volume :
110
Database :
OpenAIRE
Journal :
The Journal of Chemical Physics
Accession number :
edsair.doi...........f2221e6578526b37557b71c579d97b8a
Full Text :
https://doi.org/10.1063/1.479139