Dichalcogenide bonding in seven alkali-metal actinide chalcogenides of the KTh2Se6 structure type

Daniel E. Bugaris, Daniel M. Wells, Jiyong Yao, S. Skanthakumar, Richard G. Haire, L. Soderholm, James A. Ibers

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22 Scopus citations

Abstract

The solid-state compounds CsTh2Se6, Rb 0.85U1.74S6, RbU2Se6, TlU2Se6, Cs0.88(La0.68U 1.32)Se6, KNp2Se6, and CsNp 2Se6 of the AAn2Q6 family (A = alkali metal or Tl; An = Th, U, Np; Q = S, Se, Te) have been synthesized by high-temperature techniques. All seven crystallize in space group Immm of the orthorhombic system in the KTh2Se6 structure type. Evidence of long-range order and modulation were found in the X-ray diffraction patterns of TlU2Se6 and CsNp2Se6. A 4a×4b supercell was found for TlU2Se6 whereas a 5a×5b×5c supercell was found for CsNp2Se6. All seven compounds exhibit Q-Q interactions and, depending on the radius ratio RAn/RA, disorder of the A cation over two sites. The electrical conductivity of RbU2Se6, measured along [100], is 6×10-5 S cm-1 at 298 K. The interatomic distances, including those in the modulated structure of TlU2Se 6, and physical properties suggest the compounds may be formulated as containing tetravalent Th or U, but the formal oxidation state of Np in the modulated structure of CsNp2Se6 is less certain. The actinide contraction from Th to U to Np is apparent in the interatomic distances.

Original languageEnglish (US)
Pages (from-to)8381-8388
Number of pages8
JournalInorganic chemistry
Volume49
Issue number18
DOIs
StatePublished - Sep 20 2010

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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