Structures and phase transitions of CePd 3+xGa 8-x: New variants of the BaHg 11 structure type

Melanie C. Francisco, Christos D. Malliakas, Robin T. MacAluso, Joseph Prestigiacomo, Neel Haldolaarachchige, Philip W. Adams, David P. Young, Ying Jia, Helmut Claus, K. E. Gray, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

New distorted variants of the cubic BaHg 11 structure type have been synthesized in Ga flux. Multiple phases of CePd 3+xGa 8-x, which include an orthorhombic Pmmn structure (x = 3.21(2)), a rhombohedral R3̄m structure (x = 3.13(4)), and a cubic Fm3̄m superstructure (x = 2.69(6)), form preferentially depending on reaction cooling rate and isolation temperature. Differential thermal analysis and in situ temperature-dependent powder X-ray diffraction patterns show a reversible phase transition at approximately 640 °C between the low temperature orthorhombic and rhombohedral structures and the high temperature cubic superstructure. Single crystal X-ray diffraction experiments indicate that the general structure of BaHg 11, including the intersecting planes of a kagomé-type arrangement of Ce atoms, is only slightly distorted in the low temperature phases. A combination of Kondo, crystal electric field, and magnetic frustration effects may be present, resulting in low temperature anomalies in magnetic susceptibility, electrical resistivity, and heat capacity measurements. In addition to CePd 3+xGa 8-x, the rare earth analogues REPd 3+xGa 8-x, RE = La, Nd, Sm, Tm, and Yb, were successfully synthesized and also crystallize in one of the lower symmetry space groups.

Original languageEnglish (US)
Pages (from-to)12998-13009
Number of pages12
JournalJournal of the American Chemical Society
Volume134
Issue number31
DOIs
StatePublished - Aug 8 2012

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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