Comparative analysis for meaningful interpretation of rare-earth oxide M_4,5 energy loss edges

2021/01/17 by Ellis Kennedy, Kennedy, Ellis, Christina Choi +3
Chemistry · Materials Science · #Advanced NMR Techniques and Applications #FOS: Physical sciences #Lanthanide and Transition Metal Complexes #Magnetism in coordination complexes #Materials Science (cond-mat.mtrl-sci)

paper · pdf · doi:10.48550/arxiv.2101.06794

openalex publication_date 2021/01/17 · openalex created_date 2021/02/01 · openalex updated_date 2026/07/28

Abstract

The magnetic, electronic, and optical properties of rare earth-oxides are directly influenced by the valency of the metallic cation. With the development of next generation electron energy-loss spectrometers, high-energy lanthanide fine structure can be studied with improved signal-to-noise for quantitative analysis. Unfortunately, the behavior of rare-earth 4f orbital electrons is not well understood. To establish best practices for analysis of energy-loss spectra from lanthanide oxides, we have performed a comparative study of the four traditional white line analysis methods extended to lanthanide M_4,5 edges resulting from 3d → 4f orbital transitions using data from Gatan's EELS Atlas. The M₄/M₅ spectral feature ratios were examined as a function of 4f occupancy. The M₄/M₅ spectral feature ratio decreases exponentially as 4f occupancy increases, except for a plateau between Sm³⁺ and Dy³⁺. The full-width at half the maximum intensity of the M₄ edges shows increased broadening for Sm³⁺ through Dy³⁺. We suggest that the plateau results from 4f orbital half-filling and is explained through the relationship between electron transition probability and transition lifetime as expressed through Fermi's Golden Rule. Of the four spectral analysis methods described, only the integrated area method can be ascribed a quantitative physical interpretation.

Citations

• Intensities of Crystal Spectra of Rare-Earth Ions
• Oxidation state and chemical shift investigation in transition metal oxides by EELS

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