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Spectra, Energy Levels and Energy Transfer in High Symmetry Lanthanide Compounds

  • Chapter
Transition Metal and Rare Earth Compounds

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 241))

Abstract

The Ln3+ ion is situated at a site of octahedral symmetry in crystals of the lanthanide elpasolites, M2ALnX6. The syntheses and crystal structures of M2ALnX6 are described, with particular reference to phase transitions. The centrosymmetric environment of Ln3+ confers different spectral properties than are observed for most solid-state lanthanide ion systems, and the selection rules are deduced. The vibrational, electronic Raman and electronic spectra of the lanthanide elpasolite systems are presented and discussed. The electronic spectra are described in terms of the 4fN-4fN zero phonon line and the vibronic sideband structure and the success of intensity calculations is evaluated. The synergy of one- and two-photon studies is emphasized. The differences with the 4fN-4fN−15d spectra of M2ALnX6 are illustrated. The parametrization of the energy level datasets is assessed and the success of recent refinements is analysed. Following a brief review of the theory of energy transfer in crystals, experimental studies of quenching, cross-relaxation, upconversion and photon avalanche in neat and doped elpasolite systems are reviewed. Physical mechanisms are given for spectral features and for energy transfer pathways.

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Abbreviations

CF:

Crystal field

ED:

Electric dipole

EDV:

Electric dipole vibronic

EQ:

Electric quadrupole

ESA:

Excited state absorption

ET:

Energy transfer

IR:

Infrared

irrep:

Irreducible representation

MCD:

Magnetic circular dichroism

MCPE:

Magnetic circularly polarized emission

TP:

Two-photon

ZPL:

Zero phonon line

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Acknowledgements

This work was supported by the City University of Hong Kong Strategic Research Grant 7001199. I am indebted to Prof. Xia Shangda and Dr. Michèle Faucher for long and fruitful collaborations. I also thank my two PhD students Drs. Michael Chua and Chris Mak, and other collaborators, especially Profs. Mike Reid, Norman Edelstein and Roberto Acevedo. In addition, I thank both Prof. Xia and Dr. Faucher for carefully reading and correcting the manuscript, especially for Prof. Xia’s detailed suggestions about formulae and statements in Sects. 6–8 and 13.3.

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    Peter A. Tanner

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Appendix

Appendix

The O h point group character table and the O (and O* double group) multiplication table are given in Tables A1 and A2.

Table A1 Character table for O h molecular point group
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Table A2 Multiplication table for O and O* molecular point group (O h =O×C i )
Full size table

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Tanner, P.A. Spectra, Energy Levels and Energy Transfer in High Symmetry Lanthanide Compounds. In: Transition Metal and Rare Earth Compounds. Topics in Current Chemistry, vol 241. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b96863

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