Electronic structure and energy level schemes of RE3+

Author(s)
Ismail A. M. Ibrahim, Zoltan Lences, Pavol Sajgalik, Lubomir Benco
Abstract

First principles calculations of rare earth (RE)-doped LaSi3N5 host lattice are performed to obtain the electronic structure, the band gap (BG), and the character of electronic transitions. Doping with both trivalent and bivalent RE cations is inspected. RE 4f states form two bands of occupied and unoccupied states separated by ~5 eV. In RE3+-doped compounds 4f states are shifted by ~6 eV to more negative energies compared with RE2+-compounds. This stabilization causes that RE3+ 4f bands are in a different position relative to the valence band and the conduction band than RE2+ 4f bands and therefore different electronic transitions apply. BG of RE3+-compounds decreases from ~4.6 eV (Ce) to ~1.5 eV (Eu). Except for Ce3+, exhibiting the 4f→5d transition, other RE3+-compounds show the charge transfer of the p→4f character. BG of RE2+-compounds increases from ~0.80 eV (Ce, Pr) to ~0.95 eV (Nd, Pm), ~1.43 eV (Sm), and ~3.28 eV (Eu) and the electronic transition is of the 4f→5d character. The energy level scheme constructed from ab initio calculated electronic structures agrees well with the experimental energy level diagram. The agreement demonstrates the reliability of the hybrid functional HSE06 to describe correctly bands of nonbonding RE 4f electrons.

Organisation(s)
Computational Materials Physics
External organisation(s)
Slovak Academy of Sciences (SAS)
Journal
Journal of Luminescence
Volume
164
Pages
131-137
No. of pages
7
ISSN
0022-2313
DOI
https://doi.org/10.1016/j.jlumin.2015.03.035
Publication date
08-2015
Peer reviewed
Yes
Austrian Fields of Science 2012
103025 Quantum mechanics, 103036 Theoretical physics, 103015 Condensed matter, 103009 Solid state physics
Keywords
ASJC Scopus subject areas
Condensed Matter Physics, Atomic and Molecular Physics, and Optics, General Chemistry, Biophysics, Biochemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/0f758593-c4fe-4059-bfb7-551b9cd76f5c