The valence state of uranium in K6Cu12U 2S15

H. Schilder, M. Speldrich, H. Lueken, A. C. Sutorik, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The paramagnetic behaviour of K6Cu12U 2S15 has been analysed, regarding copper as diamagnetic (Cu+), sulfur as mixed-valent S2-/S- with magnetically silent delocalized S- holes in the valence band, and the actinide as either U5+[5f1] or U4+[5f 2] in trigonally distorted octahedral surrounding (pseudosymmetry 3̄m) of sulfur. Fitting procedures have been carried out, accounting for spin-orbit coupling, ligand-field potential (parameters Bk q), interelectronic repulsion (for U4+[5f2]), cooperative magnetic effects (molecular field parameter λ), and applied magnetic field. Keeping the ratios B43/B4 0, B63/B60, B 66/B60 on their point charge electrostatic values with respect to the sulfur ligands, the three axial parameters Bk0 (k=2,4,6) and λ were refined. Agreement between measured and calculated susceptibility data was obtained for U5+ with Bk0 values expected for octahedral surrounding and λ4+ model does yield a fit of comparable quality, but gives B k0 values that are unreasonable with respect to sign and magnitude. To conclude, on the basis of the magnetic properties the title compound is a 5f1 system corresponding to the elements formal charges (K+)6(Cu+)12(U5+) 2(S2-)13(S-)2.

Original languageEnglish
Pages (from-to)249-252
Number of pages4
JournalJournal of Alloys and Compounds
Volume374
Issue number1-2
DOIs
Publication statusPublished - Jul 14 2004

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Uranium
Sulfur
Actinoid Series Elements
Ligands
Actinides
Valence bands
Copper
Electrostatics
Magnetic properties
Orbits
Magnetic fields

Keywords

  • Actinide
  • KCuUS
  • Magnetic properties
  • Mixed-valent S/S

ASJC Scopus subject areas

  • Metals and Alloys

Cite this

The valence state of uranium in K6Cu12U 2S15. / Schilder, H.; Speldrich, M.; Lueken, H.; Sutorik, A. C.; Kanatzidis, Mercouri G.

In: Journal of Alloys and Compounds, Vol. 374, No. 1-2, 14.07.2004, p. 249-252.

Research output: Contribution to journalArticle

Schilder, H, Speldrich, M, Lueken, H, Sutorik, AC & Kanatzidis, MG 2004, 'The valence state of uranium in K6Cu12U 2S15', Journal of Alloys and Compounds, vol. 374, no. 1-2, pp. 249-252. https://doi.org/10.1016/j.jallcom.2003.11.113
Schilder, H. ; Speldrich, M. ; Lueken, H. ; Sutorik, A. C. ; Kanatzidis, Mercouri G. / The valence state of uranium in K6Cu12U 2S15. In: Journal of Alloys and Compounds. 2004 ; Vol. 374, No. 1-2. pp. 249-252.
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