Controlled Phonon Transport via Chemical Bond Stretching and Defect Engineering: The Case Study of Filled β-Mn-Type Phases.

Controlling the elastic properties of the material could become a powerful tool for tuning the thermal transport in solids. Nevertheless, the impact of the crystal structure, chemical bonding, and elastic properties on the lattice thermal conductivity remains to be elucidated. This is a pivotal issue for the advancement of thermoelectric (TE) materials.

On Chemical Bonding in -GaRh and Its Effect on Structural Organization and Thermoelectric Behavior.

In the course of systematic studies of intermetallic compounds GaTM (TM─transition metal), the compound GaRh is synthesized by direct reaction of the elements at 700 °C. The material obtained is characterized as a high-temperature modification of GaRh. Powder and single-crystal X-ray diffraction analyses reveal tetragonal symmetry (space group 4/, No.

Lone-Pair-Like Interaction and Bonding Inhomogeneity Induce Ultralow Lattice Thermal Conductivity in Filled β-Manganese-Type Phases.

Finding a way to interlink heat transport with the crystal structure and order/disorder phenomena is crucial for designing materials with ultralow lattice thermal conductivity. Here, we revisit the crystal structure and explore the thermoelectric properties of several compounds from the family of the filled β-Mn-type phases GaTe ( = Pb, Sn, Ca, Na, Na + Ag). The strongly disturbed thermal transport observed in the investigated materials originates from a three-dimensional Te-Ga network with lone-pair-like interactions, which results in large variations of the Ga-Te and -Te interatomic distances and substantial anharmonic effects.

The Intermetallic Semiconductor -IrGa: a Material in the State.

The compound IrGa was synthesized by direct reaction of the elements. It is formed as a high-temperature phase in the Ir-Ga system. Single-crystal X-ray diffraction analysis confirms the tetragonal symmetry (space group 4 , No.

Phase Equilibria and Thermoelectric Properties in the Pb-Ga-Te System in the Vicinity of the PbGaTe Phase.

PbGaTe is a promising thermoelectric (TE) material due to its ultralow thermal conductivity and moderated values of the Seebeck coefficient. However, the reproducible synthesis of the PbGaTe-based materials for the investigation and tailoring of physical properties requires detailed knowledge of the phase diagram of the system. With this aim, a combined thermal, structural, and microstructural study of the Pb-Ga-Te ternary system near the PbGaTe composition is presented here, in which polycrystalline samples with the compositions (PbTe)(GaTe) (0.

Thermal conductivity of PbTe-CoSb bulk polycrystalline composite: role of microstructure and interface thermal resistance.

Systematic experimental and theoretical research on the role of microstructure and interface thermal resistance on the thermal conductivity of the PbTe-CoSb3 bulk polycrystalline composite is presented. In particular, the correlation between the particle size of the dispersed phase and interface thermal resistance (Rint) on the phonon thermal conductivity (κph) is discussed. With this aim, a series of PbTe-CoSb3 polycrystalline composite materials with different particle sizes of CoSb3 was prepared.

Charge, lattice and magnetism across the valence crossover in EuIrSi single crystals.

We present a detailed study of the temperature evolution of the crystal structure, specific heat, magnetic susceptibility and resistivity of single crystals of the paradigmatic valence-fluctuating compound [Formula: see text]. A comparison to stable-valent isostructural compounds [Formula: see text] (with Eu), and [Formula: see text], (with Eu) reveals an anomalously large thermal expansion indicative of the lattice softening associated to valence fluctuations. A marked broad peak at temperatures around 65-75 K is observed in specific heat, susceptibility and the derivative of resistivity, as thermal energy becomes large enough to excite Eu into a divalent state, which localizes one f electron and increases scattering of conduction electrons.

On Fe-Fe Dumbbells in the Ideal and Real Structures of FeGa.

The intermetallic phase FeGa belongs to the rare examples of substances with transition metals where semiconducting behavior is found. The necessary electron count of 17 ve/fu can be formally derived from eight Fe-Ga and one Fe-Fe two-center-two-electron bond. The situation is reminiscent of the well-known Fe(CO) scenario, where a direct Fe-Fe two-center-two-electron bond was shown to not be present.

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.

Exchange interactions through π-π stacking in the lamellar compound [{Cu(bipy)(en)}{Cu(bipy)(H2O)}{VO3}4]n.

Structural, magnetic, and powder and single-crystal electron paramagnetic resonance (EPR) studies were performed on [{Cu(bipy)(en)}{Cu(bipy)(H(2)O)}{VO(3)}(4)](n) (bipy = 2,2'-bipyridine, en = ethylenediamine), which is a new copper-vanadium hybrid organic-inorganic compound containing Cu(II) and V(V) centers. The oxovanadium units provide an anionic scaffolding to the structure, where two types of Cu(II) coordination modes, octahedral (Cu1) and square pyramidal (Cu2), contribute to the magnetic properties. The crystal structure contains layers including Cu1 and Cu2 ions, separated by stacked arrangements of 2,2'-bipyridine molecules.

Synthesis and catalytic properties of nanoparticulate intermetallic Ga-Pd compounds.

A two-step synthesis for the preparation of single-phase and nanoparticulate GaPd and GaPd(2) by coreduction of ionic metal-precursors with LiHBEt(3) in THF without additional stabilizers is described. The coreduction leads initially to the formation of Pd nanoparticles followed by a Pd-mediated reduction of Ga(3+) on their surfaces, requiring an additional annealing step. The majority of the intermetallic particles have diameters of 3 and 7 nm for GaPd and GaPd(2), respectively, and unexpected narrow size distributions as determined by disk centrifuge measurements.

Chemical bonding in compounds of the CuAl(2) family: MnSn(2), FeSn(2) and CoSn(2).

A model for the chemical bonding in the isostructural intermetallic compounds MnSn(2), FeSn(2) and CoSn(2), crystallising in the CuAl(2)-type structure, is developed. The description is based on quantum-chemical calculations applying the electron localisability approach as well as on experimental results obtained from Raman spectroscopy, Hall effect and electrical resistivity measurements on oriented single crystals. The analysis of the chemical bonding reveals four different covalent interactions leading to the formation of interpenetrating 6(3) nets of tin and chains of transition-metal atoms T (T=Mn, Fe or Co) along [001], which are interconnected by three-centre bonds.

Electronic structure, chemical bonding, and solid-state NMR spectroscopy of the digallides of Ca, Sr, and Ba.

Combined application of (69,71)Ga NMR spectroscopy and quantum mechanical calculations reveals the chemical bonding in the digallides of Ca, Sr, and Ba. An analysis of the electron localization function (ELF) shows honeycomb-like 6(3) nets of the Ga atoms as the most prominent structural features in SrGa(2) and BaGa(2). For CaGa(2) a description of a 3+1-coordinated Ga atom is revealed by the ELF and by an analysis of interatomic distances.

Two new hybrid organic/inorganic copper(II)-oxovanadate(V) diphosphonates: [Cu2(phen)2(O3PCH2PO3)(V2O5)(H2O)] x H2O and [Cu2(phen)2(O3P(CH2)3PO3)(V2O5)] x C3H8. Synthesis, structure, and magnetic properties.

Two new hybrid organic/inorganic copper oxovanadium diphosphonates [Cu2(phen)2(O3PCH2PO3)(V2O5)(H2O)] x H2O (1) and [(Cu2(phen)2(O3P(CH2)3PO3)(V2O5)] x C3H8 (2) have been obtained by hydrothermal synthesis. The compounds are monoclinic, and they crystallize in the space group P2(1)/n with cell parameters of a = 11.788(2) A, b = 17.