论文标题

高压下Ytterbium较高氢化物的合成,结构和电导率

Synthesis, structure and electric conductivity of higher hydrides of ytterbium at high pressure

论文作者

Jaronn, Tomasz, Ying, Jianjun, Tkacz, Marek, Grzelak, Adam, Prakapenka, Vitali B., Struzhkinb, Viktor. V., Grochala, Wojciech

论文摘要

虽然大多数稀土金属很容易形成三水合,但由于填充的4F电子外壳的稳定性增加了yb(ii),只有ybh $ _ {2.67} $,正式对应于yb $^{\ rm ii} $(yb $^$^{yb $^{\ rm iii} $ h $ $ $ $ $ _4 $ _3 $ _2 ytterbium的氢化物。利用钻石砧细胞方法和同步粉X射线衍射,我们试图通过金属YB的氢化(在室温和原位加热)和YB $ _3 $ _3 $ h $ _8 $来进一步推动此极限。也已经在中性压力传输培养基PTM中研究了后者的压缩。 YB的原位加热促进了YBH $ _2 $加上X Hydride的形成,但我们尚未观察到在H $ _2 $和HE或NE PTM中压缩的系统之间存在明显的定性差异。在所有这些情况下,从P-31M对称性的单位细胞到I4/M和I4/MMM系统的相变序列发生在CA内。分别为13至18 GPA和大约27 GPA。同时,在h $ _2 $ ptm中压缩的系统的分子体积是大约。 1.5%比惰性气体压缩的大1.5%,表明少量氢的吸收。然而,向YBH $ _3 $的氢化是不完整的,并且多氢化物并未达到此处研究的最高压力。 75 GPA。正如我们在NACL PTM中压缩的电子传输测量所指出的那样,混合价YB $ _3 $ _3 $ h $ _8 $保留其半导体特征至少至少50 GPA,尽管非常低的剩余传导能量,小于5 MEV的较低的次数持续激活能力,这表明在进一步的压缩下可以实现金属化。最后,我们提供了一个假设的化学计量YBH $ _3 $的理论描述。

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$^{\rm II}$(Yb$^{\rm III}$H$_4$)$_2$ or Yb$_3$H$_8$, remains the highest hydride of ytterbium. Utilizing diamond anvil cell methodology and synchrotron powder x-ray diffraction we have attempted to push this limit further via hydrogenation of metallic Yb (at room temperature and heated in situ) and of 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$_2$ plus x hydride, we have not observed the clear qualitative differences between the systems compressed in H$_2$ and He or Ne PTM. In all these cases a sequence of phase transitions from the unit cells of P-31m symmetry to the I4/m and I4/mmm systems occurred within ca. 13 to 18 GPa and around 27 GPa, respectively. At the same time, 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 towards YbH$_3$ is incomplete, and polyhydrides do not form up to the highest pressure studied here of ca. 75 GPa. As pointed out by our electronic transport measurements under compression in NaCl PTM, the mixed-valence Yb$_3$H$_8$ retains its semiconducting character up to at least 50 GPa, although the very low remnant activation energy of conduction, smaller than 5 meV, suggests that the metallization under further compression should be achievable. Finally, we provide a theoretical description of a hypothetical stoichiometric YbH$_3$.

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