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Hydrogen order in hydrides of Laves phases

  • Holger Kohlmann EMAIL logo
Veröffentlicht/Copyright: 24. Juli 2020
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Zeitschrift für Kristallographie - Crystalline Materials
Aus der Zeitschrift Zeitschrift für Kristallographie - Crystalline Materials Band 235 Heft 8-9

Abstract

Many Laves phases AM2 takes up hydrogen to form interstitial hydrides in which hydrogen atoms partially occupy A2M2, AM3, and/or M4 tetrahedral interstices. They often exhibit temperature-driven order-disorder phase transitions, which are triggered by repulsion of hydrogen atoms occupying neighboring tetrahedral interstices. Because of the phase widths with respect to hydrogen a complete ordering, i.e., full occupation of all hydrogen positions is usually not achieved. Order-disorder transitions in Laves phase hydrides are thus phase transitions between crystal structures with different degrees of hydrogen order. Comparing the crystal structures of ordered and disordered phases reveals close symmetry relationships in all known cases. This allows new insights into the crystal chemical description of such phases and into the nature of the phase transitions. Structural relationships for over 40 hydrides of cubic and hexagonal Laves phases ZrV2, HfV2, ZrCr2, ZrCo2, LaMg2, CeMg2, PrMg2, NdMg2, SmMg2, YMn2, ErMn2, TmMn2, LuMn2, Lu0.4Y0.6Mn2 YFe2, and ErFe2 are concisely described in terms of crystallographic group-subgroup schemes (Bärnighausen trees) covering 32 different crystal structure types, 26 of which represent hydrogen-ordered crystal structures.

Keywords: Bärnighausen tree; group-subgroup relationships; Laves phases; metal hydrides; order-disorder transitions

Dedicated to Professor Dr. Ulrich Müller on the occasion of his 80th birthday.

Corresponding author: Holger Kohlmann, Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, 04103Leipzig, Germany, E-mail:

Acknowledgements

My sincere thanks goes to Prof. Dr. Hartmut Bärnighausen, Prof. Dr. H. P. Beck and Prof. Dr. U. Müller for many fruitful discussions on crystallographic group-subgroup relationships and to Hannah Kohlmann for language polishing.

  1. Author contribution: The author has accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The author declares no conflicts of interest regarding this article.

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Received: 2020-02-18
Accepted: 2020-04-27
Published Online: 2020-07-24
Published in Print: 2020-09-25

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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  12. On tungstates of divalent cations (III) – Pb5O2[WO6]
  13. Hydrogen order in hydrides of Laves phases
  14. High-pressure synthesis of SmGe3
  15. The complete series of sodium rare-earth metal(III) chloride oxotellurates(IV) Na2RE3Cl3[TeO3]4 (RE = Y, La–Nd, Sm–Lu)
  16. Structural diversity of salts of terpyridine derivatives with europium(III) located in both, cation and anion, in comparison to molecular complexes
  17. Elucidating structure–property relationships in imidazolium-based halide ionic liquids: crystal structures and thermal behavior
  18. Syntheses and crystal structures of the manganese hydroxide halides Mn5(OH)6Cl4, Mn5(OH)7I3, and Mn7(OH)10I4
  19. Site-preferential copper substitution for silicon leads to Cu-chains in the new ternary silicide Ir4−xCuSi2
  20. Syntheses and crystal structures of solvate complexes of alkaline earth and lanthanoid metal iodides with N,N-dimethylformamide
https://doi.org/10.1515/zkri-2020-0043
Schlagwörter für diesen Artikel
Bärnighausen tree; group-subgroup relationships; Laves phases; metal hydrides; order-disorder transitions

Artikel in diesem Heft

  1. Frontmatter
  2. In this issue
  3. Original papers
  4. Ulrich Müller zum 80. Geburtstag gewidmet
  5. Laboratory synthesis and characterization of Knasibfite K3Na4[SiF6]3[BF4] and the homologous Ge compound K3Na4[GeF6]3[BF4]
  6. The crystal structures of α-Rb7Sb3Br16, α- and β-Tl7Bi3Br16 and their relationship to close packings of spheres
  7. Beryllium triflates: synthesis and structure of BeL2(OTf)2 (L=H2O, THF, nBu2O)
  8. Synthesis and crystal structures of two layered Cu(I) and Ag(I) iodidometalates
  9. New mixed-valent alkali chain sulfido ferrates A1+x[FeS2] (A = K, Rb, Cs; x = 0.333–0.787)
  10. Structure solution of incommensurately modulated La6MnSb15
  11. Polymorphs of VO(PO3)2: synthesis and crystal structure refinement revisited
  12. On tungstates of divalent cations (III) – Pb5O2[WO6]
  13. Hydrogen order in hydrides of Laves phases
  14. High-pressure synthesis of SmGe3
  15. The complete series of sodium rare-earth metal(III) chloride oxotellurates(IV) Na2RE3Cl3[TeO3]4 (RE = Y, La–Nd, Sm–Lu)
  16. Structural diversity of salts of terpyridine derivatives with europium(III) located in both, cation and anion, in comparison to molecular complexes
  17. Elucidating structure–property relationships in imidazolium-based halide ionic liquids: crystal structures and thermal behavior
  18. Syntheses and crystal structures of the manganese hydroxide halides Mn5(OH)6Cl4, Mn5(OH)7I3, and Mn7(OH)10I4
  19. Site-preferential copper substitution for silicon leads to Cu-chains in the new ternary silicide Ir4−xCuSi2
  20. Syntheses and crystal structures of solvate complexes of alkaline earth and lanthanoid metal iodides with N,N-dimethylformamide
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