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The valence state of uranium in K{sub 6}Cu{sub 12}U{sub 2}S{sub 15}

Abstract

The paramagnetic behaviour of K{sub 6}Cu{sub 12}U{sub 2}S{sub 15} has been analysed, regarding copper as diamagnetic (Cu{sup +}), sulfur as mixed-valent S{sup 2-}/S{sup -} with magnetically silent delocalized S{sup -} holes in the valence band, and the actinide as either U{sup 5+}[5f{sup 1}] or U{sup 4+}[5f{sup 2}] in trigonally distorted octahedral surrounding (pseudosymmetry 3-bar) of sulfur. Fitting procedures have been carried out, accounting for spin-orbit coupling, ligand-field potential (parameters B{sup k}{sub q}), interelectronic repulsion (for U{sup 4+}[5f{sup 2}]), cooperative magnetic effects (molecular field parameter {lambda}), and applied magnetic field. Keeping the ratios B{sup 4}{sub 3}/B{sup 4}{sub 0}, B{sup 6}{sub 3}/B{sup 6}{sub 0}, B{sup 6}{sub 6}/B{sup 6}{sub 0} on their point charge electrostatic values with respect to the sulfur ligands, the three axial parameters B{sup k}{sub 0} (k=2,4,6) and {lambda} were refined. Agreement between measured and calculated susceptibility data was obtained for U{sup 5+} with B{sup k}{sub 0} values expected for octahedral surrounding and {lambda}<0 speaking for antiferromagnetic interactions. The U{sup 4+} model does yield a fit of comparable quality, but gives B{sup k}{sub 0} values that are unreasonable with respect to sign and magnitude. To conclude, on the basis of the magnetic properties the title compound is a 5f{sup 1}  More>>
Publication Date:
Jul 14, 2004
Product Type:
Journal Article
Resource Relation:
Journal Name: Journal of Alloys and Compounds; Journal Volume: 374; Journal Issue: 1-2; Conference: 5. international conference on f-elements, Geneva (Switzerland), 24-29 Aug 2003; Other Information: DOI: 10.1016/j.jallcom.2003.11.113; PII: S0925838803013367; Copyright (c) 2003 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIFERROMAGNETISM; COPPER COMPOUNDS; COPPER IONS; L-S COUPLING; LIGANDS; MAGNETIC FIELDS; MAGNETIC PROPERTIES; PARAMAGNETISM; POINT CHARGE; POTASSIUM COMPOUNDS; POTASSIUM IONS; SULFIDES; SULFUR IONS; URANIUM COMPOUNDS; URANIUM IONS; VALENCE
OSTI ID:
20712552
Country of Origin:
Netherlands
Language:
English
Other Identifying Numbers:
Journal ID: ISSN 0925-8388; JALCEU; TRN: NL05R5458026602
Submitting Site:
NLN
Size:
page(s) 249-252
Announcement Date:
May 08, 2006

Citation Formats

Schilder, H, Speldrich, M, Lueken, H, Sutorik, A C, and Kanatzidis, M G. The valence state of uranium in K{sub 6}Cu{sub 12}U{sub 2}S{sub 15}. Netherlands: N. p., 2004. Web. doi:10.1016/j.jallcom.2003.11.113.
Schilder, H, Speldrich, M, Lueken, H, Sutorik, A C, & Kanatzidis, M G. The valence state of uranium in K{sub 6}Cu{sub 12}U{sub 2}S{sub 15}. Netherlands. doi:10.1016/j.jallcom.2003.11.113.
Schilder, H, Speldrich, M, Lueken, H, Sutorik, A C, and Kanatzidis, M G. 2004. "The valence state of uranium in K{sub 6}Cu{sub 12}U{sub 2}S{sub 15}." Netherlands. doi:10.1016/j.jallcom.2003.11.113. https://www.osti.gov/servlets/purl/10.1016/j.jallcom.2003.11.113.
@misc{etde_20712552,
title = {The valence state of uranium in K{sub 6}Cu{sub 12}U{sub 2}S{sub 15}}
author = {Schilder, H, Speldrich, M, Lueken, H, Sutorik, A C, and Kanatzidis, M G}
abstractNote = {The paramagnetic behaviour of K{sub 6}Cu{sub 12}U{sub 2}S{sub 15} has been analysed, regarding copper as diamagnetic (Cu{sup +}), sulfur as mixed-valent S{sup 2-}/S{sup -} with magnetically silent delocalized S{sup -} holes in the valence band, and the actinide as either U{sup 5+}[5f{sup 1}] or U{sup 4+}[5f{sup 2}] in trigonally distorted octahedral surrounding (pseudosymmetry 3-bar) of sulfur. Fitting procedures have been carried out, accounting for spin-orbit coupling, ligand-field potential (parameters B{sup k}{sub q}), interelectronic repulsion (for U{sup 4+}[5f{sup 2}]), cooperative magnetic effects (molecular field parameter {lambda}), and applied magnetic field. Keeping the ratios B{sup 4}{sub 3}/B{sup 4}{sub 0}, B{sup 6}{sub 3}/B{sup 6}{sub 0}, B{sup 6}{sub 6}/B{sup 6}{sub 0} on their point charge electrostatic values with respect to the sulfur ligands, the three axial parameters B{sup k}{sub 0} (k=2,4,6) and {lambda} were refined. Agreement between measured and calculated susceptibility data was obtained for U{sup 5+} with B{sup k}{sub 0} values expected for octahedral surrounding and {lambda}<0 speaking for antiferromagnetic interactions. The U{sup 4+} model does yield a fit of comparable quality, but gives B{sup k}{sub 0} values that are unreasonable with respect to sign and magnitude. To conclude, on the basis of the magnetic properties the title compound is a 5f{sup 1} system corresponding to the elements formal charges (K{sup +}){sub 6}(Cu{sup +}){sub 12}(U{sup 5+}){sub 2}(S{sup 2-}){sub 13}(S{sup -}){sub 2}.}
doi = {10.1016/j.jallcom.2003.11.113}
journal = {Journal of Alloys and Compounds}
issue = {1-2}
volume = {374}
place = {Netherlands}
year = {2004}
month = {Jul}
}