The reinvestigation of the crystal structure of Ba8Ge43□3 (space group $Ia{\bar 3}d$, no. 230; a = 21.3123(5) Å; Z = 8; Pearson symbol cI408) shows a full ordering of the vacancies (□) in the germanium framework. This ordered crystal structure can be considered as a derivative of an ideal “Ba8Ge46” clathrate‐I type structure ($Pm{\bar 3}n$, a′ = a/2) in which three Ge vacancies (per formula unit) are allowed to order in a cubic superstructure with a doubled unit cell parameter (□ at the 24c site, space group $Ia{\bar 3}d$). In the resulting Ge framework, each vacancy □ is surrounded by four three‐bonded (3b)Ge‐ species. The ordering in crystals of as‐cast samples (cooled in argon atmosphere, non‐annealed) is partially disrupted. For the “as‐cast” crystals, a short‐range model is proposed based on the partial distribution of Ge on the 24c and 24d sites. From the electron balance, Ba8Ge43 can be considered as a metallic Zintl phase with four excess electrons per formula unit. The Ba8Ge43 phase is stable in the temperature range 770 ‐ 810 °C and exists in equilibrium with Ba6Ge25 and Ge. By decomposition of undercooled (metastable) Ba8Ge43, a new metastable binary BaGe˜5 phase is formed.
The europium-containing clathrate-I Eu(x)Ba(8-x)Cu(16)P(30) was synthesized from the elements. Powder X-ray diffraction in combination with energy dispersive X-ray absorption spectroscopy (EDXS) and metallographic studies showed the homogeneity range with x ≤ 1.5. Determination of the crystal structure confirmed the presence of an orthorhombic superstructure of clathrate-I and revealed that Eu atoms exclusively resided in small pentagonal-dodecahedral cages. Magnetic measurements together with X-ray absorption spectroscopy are consistent with a 4f(7) (Eu(2+)) ground state for Eu(x)Ba(8-x)Cu(16)P(30). Below 3 K the Eu moments order antiferromagnetically. Resistivity measurements revealed metallic behavior of the investigated clathrate, in line with the composition deviating from the Zintl counting scheme. Local vibrations of the guest atoms inside the cages are analyzed with the help of specific heat investigations.
A new phase, Sn(x)Pt4Sb(12-y)Sn(y), has been prepared from the elements. It exhibits a wide range of homogeneity with 0.3(2) < or = x < or = 1.0(2) and 4.2(2) < or = y < or = 7.0(2). The crystal structure and the composition were established by single-crystal and powder X-ray diffraction as well as wavelength-dispersive X-ray analysis measurements and were supported by nuclear magnetic resonance experiments. The compound is the first representative of the filled-skutterudite family with the filler atoms not located at the center of the cavity but covalently bonded to the cavity's wall, as confirmed by the analysis of chemical bonding with the electron localizability indicator. The Sn and Sb atoms share the framework site with different coordinate parameters caused by the difference in atomic size; additional tin atoms are located in the cavities of the framework. The material is a diamagnet in the whole composition range. In agreement with the calculated electronic density of states, the material reveals a metallic behavior in electronic transport. The absolute values of electrical resistivity vary with the tin-to-antimony ratio.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.