Cu3Sn - understanding the systematic absences.

The intermetallic compound Cu3Sn has previously been described as a long-period antiphase boundary superstructure of the Cu3Ti structure type. While the compound itself has been reported as a tenfold and an eightfold superstructure, ternary doped alloys show shorter repetitions. Interestingly, the diffraction patterns of these compounds show non-crystallographic absences that cannot be explained using the superstructure models. Since the compound exhibits phase broadening, these models are not satisfactory because the paucity of observed data does not allow for a refinement of the composition. Here, an alternative, superspace model in the orthorhombic space group Xmcm(0ß0)000 is proposed, with the centering vectors (0,0,0,0) and (½,0,0,½). The presence of the non-crystallographic absences is explained as a result of a dominating occupational modulation that is accompanied by a weaker displacive modulation. In consistency with the EDXS results, the composition has been refined to Cu3 + xSn from single-crystal X-ray diffraction data. It is further demonstrated that by varying the length and the direction of the modulation wavevector in the superspace model, the ternary Cu3Sn compounds and other colored hexagonal close packing (h.c.p.) structures can be produced.

Synthesis, structural characterization, and ab initio study of Cu(5+δ)In(2+x)Sb(2-x): a new B8-related structure type.

A new ternary orthorhombic compound with the formula Cu(5+δ)In(2+x)Sb(2-x), crystallizing in the space group Cmc2(1) with 36 atoms per unit cell [a = 10.1813(4) Å, b = 8.4562(4) Å, c = 7.3774(2) Å, Z = 4], has been synthesized by conventional high-temperature methods. The structure is based on the B8 archetype (NiAs/Ni(2)In) and features In/Sb ordering as well as ordering of interstitial copper. Details of the experimental study and the structural parameters of this compound are reported in the first part of the work. In the second part, ab initio calculations based on the density functional theory and the projector augmented-wave method are used to characterize the structural, thermodynamic, and phase-stability properties of the new ternary phase. The present calculations include the lattice parameters, molar volume, bulk modulus and its pressure derivative, the energy of formation from the elements, and the electronic density of states. Moreover, the present ab initio method is used to investigate the thermodynamic properties of the anti-structure Cu(5)Sb(2)In(2) compound obtained by exchanging the In and Sb Wyckoff symmetric positions.

Dumbbells of five-connected silicon atoms and superconductivity in the binary silicides MSi3 (M = Ca, Y, Lu).

The new metastable binary silicides MSi(3) (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 Si(2) 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.