Evidence for 5d-σ and 5d-π covalency in lanthanide sesquioxides from oxygen K-edge X-ray absorption spectroscopy
作者： Alison B. Altman , Joseph I. Pacold , Jian Wang , Wayne W. Lukens , Stefan G. Minasian
DOI: 10.1039/C6DT00358C
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摘要: The electronic structure in the complete series of stable lanthanide sesquioxides, Ln2O3 (Ln = La to Lu, except radioactive Pm), has been evaluated using oxygen K-edge X-ray absorption spectroscopy (XAS) with a scanning transmission microscope (STXM). experimental results agree recent synthetic, spectroscopic and theoretical investigations that provided evidence for 5d orbital involvement bonding, while confirming traditional viewpoint there is little Ln 4f O 2p mixing. However, also showed changes energy occupancy orbitals can impact mixing, leading several different bonding modes seemingly identical structures. On moving from left right periodic table, abrupt were observed intensity transitions associated antibonding states. These peak intensity, which directly related amounts closely correlated well-established trends chemical accessibility towards oxidation or reduction. unique insight by XAS discussed context physical studies on trivalent compounds.
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