Synthesis of a Cu-Filled Rh17S15 Framework: Microwave Polyol Process Versus High-Temperature Route.

Metal-rich, mixed copper-rhodium sulfide Cu3-δRh34S30 that represents a new Cu-filled variant of the Rh17S15 structure has been synthesized and structurally characterized. Copper content in the [CuRh8] cubic cluster was found to vary notably dependent on the chosen synthetic route. Full site occupancy was achieved only in nanoscaled Cu3Rh34S30 obtained by a rapid, microwave-assisted reaction of CuCl, Rh2(CH3CO2)4 and thiosemicarbazide at 300 °C in just 30 min; whereas merely Cu-deficient Cu3-δRh34S30 (2.0 ≥ δ ≥ 0.9) compositions were realized via conventional high-temperature ceramic synthesis from the elements at 950 °C. Although Cu3-δRh34S30 is metallic just like Rh17S15, the slightly enhanced metal content has a dramatic effect on the electronic properties. Whereas the Rh17S15 host undergoes a superconducting transition at 5.4 K, no signs of the latter were found for the Cu-derivatives at least down to 1.8 K. This finding is corroborated by the strongly reduced density of states at the Fermi level of the ternary sulfide and the disruption of long-range Rh-Rh interactions in favor of Cu-Rh interactions as revealed by quantum-chemical calculations.

Domain overlap matrices from plane-wave-based methods of electronic structure calculation.

Plane waves are one of the most popular and efficient basis sets for electronic structure calculations of solids; however, their delocalized nature makes it difficult to employ for them classical orbital-based methods of chemical bonding analysis. The quantum chemical topology approach, introducing chemical concepts via partitioning of real space into chemically meaningful domains, has no difficulties with plane-wave-based basis sets. Many popular tools employed within this approach, for instance delocalization indices, need overlap integrals over these domains-the elements of the so called domain overlap matrices. This article reports an efficient algorithm for evaluation of domain overlap matrix elements for plane-wave-based calculations as well as evaluation of its implementation for one of the most popular projector augmented wave (PAW) methods on the small set of simple and complex solids. The stability of the obtained results with respect to PAW calculation parameters has been investigated, and the comparison of the results with the results from other calculation methods has also been made.

Germanium Dumbbells in a New Superconducting Modification of BaGe3.

We report the high-pressure high-temperature synthesis (P = 15 GPa, T = 1300 K) of BaGe3(tI32) adopting a CaGe3-type crystal structure. Bonding analysis reveals layers of covalently bonded germanium dumbbells being involved in multicenter Ba-Ge interactions. Physical measurements evidence metal-type electrical conductivity and a transition to a superconducting state at 6.5 K. Chemical bonding and physical properties of the new modification are discussed in comparison to the earlier described hexagonal form BaGe3(hP8) with a columnar arrangement of Ge3 triangles.

On the transferability of electron density in binary vanadium borides VB, V3B4 and VB2.

Binary vanadium borides are suitable model systems for a systematic analysis of the transferability concept in intermetallic compounds due to chemical intergrowth in their crystal structures. In order to underline this structural relationship, topological properties of the electron density in VB, V3B4 and VB2 reconstructed from high-resolution single-crystal X-ray diffraction data as well as derived from quantum chemical calculations, are analysed in terms of Bader's Quantum Theory of Atoms in Molecules [Bader (1990). Atoms in Molecules: A Quantum Theory, 1st ed. Oxford: Clarendon Press]. The compounds VB, V3B4 and VB2 are characterized by a charge transfer from the metal to boron together with two predominant atomic interactions, the shared covalent B-B interactions and the polar covalent B-M interactions. The resembling features of the crystal structures are well reflected by the respective B-B interatomic distances as well as by ρ(r) values at the B-B bond critical points. The latter decrease with an increase in the corresponding interatomic distances. The B-B bonds show transferable electron density properties at bond critical points depending on the respective bond distances.

A metallic room-temperature oxide ion conductor.

Nanoparticles of Bi3 Ir, obtained from a microwave-assisted polyol process, activate molecular oxygen from air at room temperature and reversibly intercalate it as oxide ions. The closely related structures of Bi3 Ir and Bi3 IrOx (x≤2) were investigated by X-ray diffraction, electron microscopy, and quantum-chemical modeling. In the topochemically formed metallic suboxide, the intermetallic building units are fully preserved. Time- and temperature-dependent monitoring of the oxygen uptake in an oxygen-filled chamber shows that the activation energy for oxide diffusion (84 meV) is one order of magnitude smaller than that in any known material. Bi3 IrOx is the first metallic oxide ion conductor and also the first that operates at room temperature.

Electron localizability indicators from spinor wavefunctions.

For the fully relativistic 4-component many-electron wavefunction six flavors of electron localizability indicators (ELI) have been proposed. Their counterparts, suitable for the application to the 2-component wavefunctions, have been also derived. Six proposed indicators have been tested on Ar and Rn atoms and one of them, the ELI-D for spatially antisymmetrized electron pairs, has been found to reveal atomic shell structures at quantitative level. Shell structures of all the atoms of periods 4-7 of the periodic table have been obtained using this indicator and compared with these obtained from the nonrelativistic limit calculations as well as from scalar-relativistic (zero-order regular approximation) calculations.

Domain-averaged Fermi-hole analysis for solids.

The domain-averaged Fermi hole (DAFH) orbitals provide highly visual representation of bonding in terms of orbital-like functions with attributed occupation numbers. It was successfully applied on many molecular systems including those with non-trivial bonding patterns. This article reports for the first time the extension of the DAFH analysis to the realm of extended periodic systems. Simple analytical model of DAFH orbital for single-band solids is introduced which allows to rationalize typical features that DAFH orbitals for extended systems may possess. In particular, a connection between Wannier and DAFH orbitals has been analyzed. The analysis of DAFH orbitals on the basis of DFT calculations is applied to hydrogen lattices of different dimensions as well as to the solids diamond, graphite, Na, Cu and NaCl. In case of hydrogen lattices, remarkable similarity is found between the DAFH orbitals evaluated with both the analytical approach and DFT. In case of the selected ionic and covalent solids the DAFH orbitals deliver bonding descriptions, which are compatible with classical orbital interpretation. For metals the DAFH analysis shows essential multicenter nature of bonding.

Electron localization and delocalization indices for solids.

The electron localization and delocalization indices obtained by the integration of exchange-correlation part of pair density over chemically meaningful regions of space, e.g., QTAIM atoms are valuable tools for the bonding analysis in molecular systems. However, among periodic systems only few simplest models were analyzed with this approach until now. This contribution reports implementation and evaluation of the localization and delocalization indices on the basis of solid state DFT calculations. A comparison with the results of simple analytical model of Ponec was made. In addition, a small set of compounds with ionic (NaCl), covalent (diamond, graphite), and metallic (Na, Cu) bonding interactions was characterized using this method. Typical features of different types of bonding were discussed using the delocalization indices.

Neutral tellurium rings in the coordination polymers [Ru(Te9)](InCl4)2, [Ru(Te8)]Cl2, and [Rh(Te6)]Cl3.

Shiny black, air-insensitive crystals of tellurium-rich one-dimensional coordination polymers were synthesized by melting a mixture of the elements with TeCl(4). The compounds [Ru(Te(9))](InCl(4))(2) and [Ru(Te(8))]Cl(2) crystallize in the monoclinic space group type C2/c, whereas [Rh(Te(6))]Cl(3) adopts the trigonal space group type R ̅3c. In the crystal structures, linear, positively charged [M(m+) (Te(n)(±0))] (M=Ru, m=2; Rh, m=3) chains run parallel to the c axes. Each of the uncharged Te(n) molecules (n=6, 8, 9) coordinates two transition-metal atoms as a bridging bis-tridentate ligand. Because the coordinating tellurium atoms act as electron-pair donors, the 18-electron rule is fulfilled for the octahedrally coordinated transition-metal cations. Based on DFT calculations, the quantum theory of atoms in molecules (QTAIM) and the electron localizability indicator (ELI) provide insight into the principles of the polar donor bonding in these complexes. Comparison with optimized ring geometries reveals substantial tension in the coordinating tellurium molecules.

Reduction of the host cationic framework charge by isoelectronic substitution: synthesis and structure of Hg7Ag2P8X6 (X = Br, I) and Hg6Ag4P8Br6.

The first compounds, Hg(7)Ag(2)P(8)X(6) (X = Br, I) and Hg(6)Ag(4)P(8)Br(6), featuring the partial isoelectronic substitution of Hg(2+) for Ag(1+) in mercury-pnicogen frameworks have been obtained and structurally characterized. The new compounds are the supramolecular assemblies built of the covalently bonded metal-pnicogen frameworks trapping guests of different complexity. The frameworks feature the perfect ordering of Hg(2+) and Ag(1+) cations and contain P(2)(4)(-) and P(6)(6)(-) phosphorus clusters. The substitution of Hg(2+) with Ag(1+) leads to the reduction in charge of the host cluster-containing cationic matrix and concomitant replacement of the monatomic X(-) guest by a lesser amount of the AgBr(3)(2)(-) anions.