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First-principles analysis method for the multiplet structures of rare-earth ions in solids

Journal of Alloys and Compounds
Publication Date
DOI: 10.1016/j.jallcom.2004.03.040
  • First-Principles Calculation
  • Fully Relativistic Calculation
  • Molecular Orbitals
  • Multiplet Structures
  • Optical Absorption Spectra


Abstract A first-principles fully relativistic multielectron method based on molecular orbital (MO) theory is applied to the analysis for the 4f5d configurations of Pr 3+-doped LaF 3, LiYF 4 (YLF), and CaF 2 crystals. The formation of MOs between the Pr 5d orbitals and the ligand fluorine 2p orbitals is considered using a (PrF 11) 8− and (PrF 8) 5− molecular models. The energy of the lowest level of 4f5d configuration decreases in the order LaF 3, LiYF 4, and CaF 2 (O h symmetry). The high energy in Pr 3+:LaF 3 is ascribed to the smaller ligand-field splitting due to the large coordination number. The analysis of many-electron wave functions shows the mixtures between the spin-orbit splitting of the 4f-level MOs and the ligand-field splitting of the 5d-level MOs. Configuration interaction with one-electron excitations gives transition probability to the originally forbidden two-electron excitations, which produce satellite structures in spectra.

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