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Title: REAuAl{sub 4}Ge{sub 2} and REAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (RE=rare earth element): Quaternary intermetallics grown in liquid aluminum

Abstract

The two families of intermetallic phases REAuAl{sub 4}Ge{sub 2} (1) (RE=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb) and REAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (2) (x=0.4) (RE=Ce and Eu) were obtained by the reactive combination of RE, Au and Ge in liquid aluminum. The structure of (1) adopts the space group R-3m (CeAuAl{sub 4}Ge{sub 2}, a=4.2384(7)A, c=31.613(7)A; NdAuAl{sub 4}Ge{sub 2}, a=4.2258(4)A, c=31.359(5)A; GdAuAl{sub 4}Ge{sub 2}, a=4.2123(6)A, c=30.994(6)A; ErAuAl{sub 4}Ge{sub 2}, a=4.2074(4)A, c=30.717(5)A). The structure of (2) adopts the tetragonal space group P4/mmm with lattice parameters: a=4.3134(8)A, c=8.371(3)A for EuAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (x=0.4). Both structure types present slabs of ''AuAl{sub 4}Ge{sub 2}'' or ''AuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2}'' stacking along the c-axis with layers of RE atoms in between. Magnetic susceptibility measurements indicate that the RE atoms (except for Ce and Eu) possess magnetic moments consistent with +3 species. The Ce atoms in CeAuAl{sub 4}Ge{sub 2} and CeAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (x=0.4) appear to be in a mixed +3/+4 valence state; DyAuAl{sub 4}Ge{sub 2} undergoes an antiferromagnetic transition at 11K and below this temperature exhibits metamagnetic behavior. The Eu atoms in EuAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (x=0.4) appear to be in a 2+ oxidationmore » state.« less

Authors:
 [1];  [2]
  1. Department of Chemistry, Michigan State University, East Lansing, Michigan 48824 (United States)
  2. Department of Chemistry, Michigan State University, East Lansing, Michigan 48824 (United States). E-mail: kanatzidis@chemistry.msu.edu
Publication Date:
OSTI Identifier:
20784755
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 178; Journal Issue: 11; Other Information: DOI: 10.1016/j.jssc.2005.07.029; PII: S0022-4596(05)00346-4; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALUMINIUM; ALUMINIUM COMPOUNDS; ANTIFERROMAGNETISM; FLUX SYNTHESIS; GERMANIUM COMPOUNDS; GOLD COMPOUNDS; INTERMETALLIC COMPOUNDS; LATTICE PARAMETERS; LAYERS; LIQUIDS; MAGNETIC MOMENTS; MAGNETIC SUSCEPTIBILITY; RARE EARTH COMPOUNDS; SPACE GROUPS; TETRAGONAL LATTICES

Citation Formats

Wu Xiuni, and Kanatzidis, Mercouri G. REAuAl{sub 4}Ge{sub 2} and REAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (RE=rare earth element): Quaternary intermetallics grown in liquid aluminum. United States: N. p., 2005. Web.
Wu Xiuni, & Kanatzidis, Mercouri G. REAuAl{sub 4}Ge{sub 2} and REAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (RE=rare earth element): Quaternary intermetallics grown in liquid aluminum. United States.
Wu Xiuni, and Kanatzidis, Mercouri G. Tue . "REAuAl{sub 4}Ge{sub 2} and REAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (RE=rare earth element): Quaternary intermetallics grown in liquid aluminum". United States. doi:.
@article{osti_20784755,
title = {REAuAl{sub 4}Ge{sub 2} and REAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (RE=rare earth element): Quaternary intermetallics grown in liquid aluminum},
author = {Wu Xiuni and Kanatzidis, Mercouri G.},
abstractNote = {The two families of intermetallic phases REAuAl{sub 4}Ge{sub 2} (1) (RE=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm and Yb) and REAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (2) (x=0.4) (RE=Ce and Eu) were obtained by the reactive combination of RE, Au and Ge in liquid aluminum. The structure of (1) adopts the space group R-3m (CeAuAl{sub 4}Ge{sub 2}, a=4.2384(7)A, c=31.613(7)A; NdAuAl{sub 4}Ge{sub 2}, a=4.2258(4)A, c=31.359(5)A; GdAuAl{sub 4}Ge{sub 2}, a=4.2123(6)A, c=30.994(6)A; ErAuAl{sub 4}Ge{sub 2}, a=4.2074(4)A, c=30.717(5)A). The structure of (2) adopts the tetragonal space group P4/mmm with lattice parameters: a=4.3134(8)A, c=8.371(3)A for EuAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (x=0.4). Both structure types present slabs of ''AuAl{sub 4}Ge{sub 2}'' or ''AuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2}'' stacking along the c-axis with layers of RE atoms in between. Magnetic susceptibility measurements indicate that the RE atoms (except for Ce and Eu) possess magnetic moments consistent with +3 species. The Ce atoms in CeAuAl{sub 4}Ge{sub 2} and CeAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (x=0.4) appear to be in a mixed +3/+4 valence state; DyAuAl{sub 4}Ge{sub 2} undergoes an antiferromagnetic transition at 11K and below this temperature exhibits metamagnetic behavior. The Eu atoms in EuAuAl{sub 4}(Au{sub x}Ge{sub 1-x}){sub 2} (x=0.4) appear to be in a 2+ oxidation state.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 11,
volume = 178,
place = {United States},
year = {Tue Nov 15 00:00:00 EST 2005},
month = {Tue Nov 15 00:00:00 EST 2005}
}
  • Investigations on phase relationships and crystal structures have been conducted on several ternary rare-earth titanium antimonide systems. The isothermal cross-sections of the ternary RE-Ti-Sb systems containing a representative early (RE=La) and late rare-earth element (RE=Er) have been constructed at 800 deg. C. In the La-Ti-Sb system, the previously known compound La{sub 3}TiSb{sub 5} was confirmed and the new compound La{sub 2}Ti{sub 7}Sb{sub 12} (own type, Cmmm, Z=2, a=10.5446(10) A, b=20.768(2) A, and c=4.4344(4) A) was discovered. In the Er-Ti-Sb system, no ternary compounds were found. The structure of La{sub 2}Ti{sub 7}Sb{sub 12} consists of a complex arrangement of TiSb{sub 6}more » octahedra and disordered fragments of homoatomic Sb assemblies, generating a three-dimensional framework in which La atoms reside. Other early rare-earth elements (RE=Ce, Pr, Nd) can be substituted in this structure type. Attempts to prepare crystals in these systems through use of a tin flux resulted in the discovery of a new Sn-containing pseudoternary phase RETi{sub 3}(Sn{sub x}Sb{sub 1-x}){sub 4} for RE=Nd, Sm (own type, Fmmm, Z=8; a=5.7806(4) A, b=10.0846(7) A, and c=24.2260(16) A for NdTi{sub 3}(Sn{sub 0.1}Sb{sub 0.9}){sub 4}; a=5.7590(4) A, b=10.0686(6) A, and c=24.1167(14) A for SmTi{sub 3}(Sn{sub 0.1}Sb{sub 0.9}){sub 4}). Its structure consists of double-layer slabs of Ti-centred octahedra stacked alternately with nets of the RE atoms; the Ti atoms are arranged in kagome nets. - Graphical abstract: La{sub 2}Ti{sub 7}Sb{sub 12} contains sectioned layers consisting of Ti-centred octahedra linked by corner- and face-sharing.« less
  • Four novel intermetallic silicides, RE5Mn4Al23–xSix (x = 7.9(9), RE = Ho, Er, Yb) and Er44Mn55(AlSi)237, have been prepared by reaction in aluminum flux. Three RE5Mn4Al23–xSix compounds crystallize in the tetragonal space group P4/mmm with the relatively rare Gd5Mg5Fe4Al18–xSix structure type. Refinement of single-crystal X-ray diffraction data yielded unit cell parameters of a = 11.3834(9)–11.4171(10) Å and c = 4.0297(2)–4.0575(4) Å with volumes ranging from 522.41(5) to 528.90(8) Å3. Structure refinements on single-crystal diffraction data show that Er44Mn55(AlSi)237 adopts a new cubic structure type in the space group Pm3n with a very large unit cell edge of a = 21.815(3) Å.more » This new structure is best understood when viewed as two sets of nested polyhedra centered on a main group atom and a manganese atom. These polyhedral clusters describe the majority of the atomic positions in the structure and form a perovskite-type network. We also report the electrical and magnetic properties of the title compounds. All compounds except the Ho analogue behave as normal paramagnetic metals without any observed magnetic transitions above 5 K and exhibit antiferromagnetic correlations deduced from the value of their Curie constants. Ho5Mn4Al23–xSix exhibits a ferromagnetic transition at 20 K and an additional metamagnetic transition at 10 K, suggesting independent ordering temperatures for two distinct magnetic sublattices.« less
  • Reactions of the elements at 800 °C with the nominal compositions REAg{sub 1−x}Zn{sub x}As{sub 2} resulted in quaternary arsenides REAg{sub 1−x}Zn{sub y}As{sub 2} in which the combined Ag and Zn content deviates increasingly from unity in the Zn-richer phases, reflecting the transition from the fully stoichiometric ternary silver-containing arsenides REAgAs{sub 2} to the substoichiometric zinc-containing ones REZn{sub 0.67}As{sub 2}. Powder X-ray diffraction analysis indicated SrZnBi{sub 2}-type (space group I4/mmm, Z=4; RE=La, Ce) and HfCuSi{sub 2}-type structures (space group P4/nmm, Z=2; RE=Pr, Nd, Sm, Gd, Tb, Dy). Single-crystal X-ray diffraction analysis performed on LaAg{sub 0.5}Zn{sub 0.5}As{sub 2}, PrAg{sub 0.5}Zn{sub 0.5}As{sub 2},more » and NdAg{sub 0.5}Zn{sub 0.5}As{sub 2} indicated that the Ag and Zn atoms are disordered within metal-centred tetrahedra and provided no evidence for distortion of the square As nets. The small electron excess tolerated in these quaternary arsenides and the absence of distortion in the square nets can be traced to the occurrence of As–As states that are only weakly antibonding near the Fermi level. PrAg{sub 0.5}Zn{sub 0.5}As{sub 2} and NdAg{sub 0.5}Zn{sub 0.5}As{sub 2} are paramagnetic with effective magnetic moments consistent with trivalent RE species. - Graphical abstract: On proceeding from fully stoichiometric REAgAs{sub 2} to substoichiometric REZn{sub 0.67}As{sub 2}, deficiencies in Zn content become increasingly prominent in quaternary arsenides REAg{sub 1−x}Zn{sub y}As{sub 2}. - Highlights: • Ag and Zn atoms are disordered within quaternary arsenides REAg{sub 1−x}Zn{sub y}As{sub 2}. • In Zn-richer phases, Zn deficiencies develop to counteract electron excess. • Distortions of square As net appear to be suppressed.« less