Cargando…
Synthesis, Structure, and Electric Conductivity of Higher Hydrides of Ytterbium at High Pressure
[Image: see text] While most of the rare-earth metals readily form trihydrides, due to increased stability of the filled 4f electronic shell for Yb(II), only YbH(2.67), formally corresponding to Yb(II)(Yb(III)H(4))(2) (or Yb(3)H(8)), remains the highest hydride of ytterbium. Utilizing the diamond an...
Autores principales: | , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9490838/ https://www.ncbi.nlm.nih.gov/pubmed/35642313 http://dx.doi.org/10.1021/acs.inorgchem.2c00405 |
Sumario: | [Image: see text] While most of the rare-earth metals readily form trihydrides, due to increased stability of the filled 4f electronic shell for Yb(II), only YbH(2.67), formally corresponding to Yb(II)(Yb(III)H(4))(2) (or Yb(3)H(8)), remains the highest hydride of ytterbium. Utilizing the diamond anvil cell methodology and synchrotron powder X-ray diffraction, we have attempted to push this limit further via hydrogenation of metallic Yb and Yb(3)H(8). Compression of the latter has also been investigated in a neutral pressure-transmitting medium (PTM). While the in situ heating of Yb facilitates the formation of YbH(2+x) hydrides, we have not observed clear qualitative differences between the systems compressed in H(2) and He or Ne PTM. In all of these cases, a sequence of phase transitions occurred within ca. 13–18 GPa (P3̅1m–I4/m phase) and around 27 GPa (to the I4/mmm phase). The molecular volume of the systems compressed in H(2) PTM is ca. 1.5% larger than of those compressed in inert gases, suggesting a small hydrogen uptake. Nevertheless, hydrogenation toward YbH(3) is incomplete, and polyhydrides do not form up to the highest pressure studied here (ca. 75 GPa). As pointed out by electronic transport measurements, the mixed-valence Yb(3)H(8) retains its semiconducting character up to >50 GPa, although the very low remnant activation energy of conduction (<5 meV) suggests that metallization under further compression should be achievable. Finally, we provide a theoretical description of a hypothetical stoichiometric YbH(3). |
---|