Chemical effects of high‐resolution YbLγ4 emission spectra: a possible probe for chemical analysis. (23rd July 2013)

• Record Type: Journal Article
• Authors: Hayashi, Hisashi; Kanai, Noriko; Kawamura, Naomi; Matsuda, Yasuhiro H.; Kuga, Kentaro; Nakatsuji, Satoru; Yamashita, Tetsuro; Ohara, Shigeo
• Is Part Of: X-ray spectrometry. Volume 42:Number 6(2013:Nov./Dec.)
• Page Start: 450
• Page End: 455
• Publication Date: 2013-07-23
• Subjects: X-ray spectroscopy -- Periodicals; 543.62
• DOI: 10.1002/xrs.2502
• Languages: English
• ISSNs: 0049-8246

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>An 'eccentric' X‐ray emission, Yb<italic>Lγ</italic><sub>4</sub>, was measured for Yb metal, Yb<sub>2</sub>O<sub>3</sub>, YbF<sub>3</sub>, <italic>β</italic>‐YbAlB<sub>4</sub>, YbNi<sub>3</sub>Al<sub>9</sub>, and YbNi<sub>3</sub>Ga<sub>9</sub> with a resolution of ~0.9 eV. Peak splitting of the Yb<italic>Lγ</italic><sub>4</sub> line was observed in all the recorded spectra and was attributed to the two components originating from the <italic>LS</italic> coupling of the Yb5p hole, the Yb5p<sub>1/2</sub> (<italic>L</italic><sub>I</sub><italic>O</italic><sub>II</sub>: <italic>Lγ</italic><sub>4</sub>′) and Yb5p<sub>3/2</sub> components (<italic>L</italic><sub>I</sub><italic>O</italic><sub>III</sub>: <italic>Lγ</italic><sub>4</sub>). The spectra were substantially different depending on the chemical environment of Yb. The position of the <italic>Lγ</italic><sub>4</sub> + <italic>Lγ</italic><sub>4</sub>′ band shifts depending on the valence of Yb (<italic>v</italic>): ~4.4 eV from divalent to trivalent. The <italic>Lγ</italic><sub>4</sub> + <italic>Lγ</italic><sub>4</sub>′ spectra of the mixed valence intermetallics, i.e. YbNi<sub>3</sub>Ga<sub>9</sub> (<italic>v</italic> = 2.59) and <italic>β</italic>‐YbAlB<sub>4</sub> (<italic>v</italic> = 2.75), were fairly well reproduced by averaging the spectra of divalent Yb and trivalent YbNi<sub>3</sub>Al<sub>9</sub>, which suggests the possibility of using the Yb<italic>Lγ</italic><sub>4</sub> emission for determining the valence of Yb intermetallics. In trivalent Yb compounds, the relative intensity of <italic>Lγ</italic><sub>4</sub> compared with that of <italic>Lγ</italic><sub>4</sub>′, as well as the appearance of a high‐energy satellite, was found to be influenced by the ligands around the Yb ions. With the aid of preliminary atomic multiplet and band structure calculations, the differences in the valence band structure and resultant screening effects on the <italic>O</italic><sub>II, III</sub><sup>−1</sup> states were determined to be the possible causes for the observed ligand dependence. © 2013 The Authors. <italic>X‐ray spectrometry</italic> published by John Wiley & Sons, Ltd.</p> </abstract>