Dumbbells of Five-Connected Ge Atoms and Superconductivity in CaGe₃

CaGe₃ has been synthesized at high-pressure, high-temperature conditions. The atomic pattern comprises intricate germanium layers of condensed moleculelike dimers. Below <i>T</i>_c = 6.8 K, type II superconductivity with moderately strong electron–phonon coupling is observed

Cluster Formation in the Superconducting Complex Intermetallic Compound Be₂₁Pt₅

ConspectusMaterials with the crystal structure of γ-brass type (Cu₅Zn₈ type) are typical representatives of intermetallic compounds. From the electronic point of view, they are often interpreted using the valence electron concentration approach of Hume–Rothery, developed previously for transition metals. The γ-brass-type phases of the main-group elements are rather rare. The intermetallic compound Be₂₁Pt₅, a new member of this family, was synthesized, and its crystal structure, chemical bonding, and physical properties were characterized.Be₂₁Pt₅ crystallizes in the cubic space group <i>F</i>4̅3<i>m</i> with lattice parameter <i>a</i> = 15.90417(3) Å and 416 atoms per unit cell. From the crystallographic point of view, the binary substance represents a special family of intermetallic compounds called complex metallic alloys (CMA). The crystal structure was solved by a combination of synchrotron and neutron powder diffraction data. Besides the large difference in the scattering power of the components, the structure solution was hampered by the systematic presence of very weak reflections mimicking wrong symmetry. The structural motif of Be₂₁Pt₅ is described as a 2 × 2 × 2 superstructure of the γ-brass structure (Cu₅Zn₈ type) or 6 × 6 × 6 superstructure of the simple bcc structural pattern with distinct distribution of defects. The main building elements of the crystal structure are four types of nested polyhedral units (clusters) with the compositions Be₂₂Pt₄ and Be₂₀Pt₆. Each cluster contains four shells (4 + 4 + 6 + 12 atoms). Clusters with different compositions reveal various occupation of the shells by platinum and beryllium. Polyhedral nested units with the same composition differ by the distance of the shell atoms to the cluster center.Analysis of chemical bonding was made applying the electron localizability approach, a quantum chemical technique operating in real space that is proven to be especially efficient for intermetallic compounds. Evaluations of the calculated electron density and electron localizability indicator (ELI-D) revealed multicenter bonding, being in accordance with the low valence electron count per atom in Be₂₁Pt₅. A new type of atomic interactions in intermetallic compounds, cluster bonds involving 8 or even 14 atoms, is found in the clusters with shorter distances between the shell atoms and the cluster centers. In the remaining clusters, four- and five-center bonds characterize the atomic interactions. Multicluster interactions within the polyhedral nested units and three-center polar intercluster bonds result in a three-dimensional framework resembling the structural pattern of NaCl. Be₂₁Pt₅ is a diamagnetic metal and one of rather rare CMA compounds revealing superconductivity (<i>T</i>_c = 2.06 K)

Dumbbells of Five-Connected Silicon Atoms and Superconductivity in the Binary Silicides MSi₃ (M = Ca, Y, Lu)

The new metastable binary silicides MSi₃ (M = Ca, Y, Lu) have been synthesized by high-pressure, high-temperature reactions at pressures between 12(2) and 15(2) GPa and temperatures from 900(100) to 1400(150) K. The atomic patterns comprise intricate silicon layers of condensed molecule-like Si₂ dimers. The alkaline-earth element adopts the oxidation state +2, while the rare-earth and transition metals realize +3. All of the compounds exhibit BCS-type superconductivity with weak electron–phonon coupling below critical temperatures of up to 7 K