Double Helix of Icosahedra Structure and Spin Glass Magnetism of the δ-Co2.5Zn17.5-xMnx (x = 0.4-3.5) Pseudo-Binary Alloys.

We have synthesized δ-Co2.5Zn17.5-xMnx (x = 0.4-3.5) pseudo-binary alloys of 10 different compositions by a high-temperature solid-state synthetic route, determined their crystal structures and the Mn substitution pattern, and estimated the existence range of the δ-phase. The alloys crystallize in two chiral enantiomorphic space groups P62 and P64, where the basic atomic polyhedron of the chiral structure is an icosahedron and the neighboring icosahedra share vertices to form an infinitely long double helix along the hexagonal axis (like in the δ-Co2.5Zn17.5 parent binary phase). The alloys are pure δ-phase up to the Mn content x ≈ 3.5. The Mn atoms partially substitute Zn atoms at particular crystallographic sites located on the icosahedra. The study of magnetism was performed on the Co2.5Zn17.1Mn0.4 alloy with the lowest Mn content. Contrary to the expectation that structural chirality may induce the formation of a nontrivial magnetic state, a spin glass state with no relation to the structural chirality was found. The magnetic sublattice contains all of the necessary ingredients (randomness and frustration) for the formation of a spin glass state. Typical out-of-equilibrium dynamic phenomena of a spin system with broken ergodicity were detected below the spin freezing temperature Tf ≈ 8 K.

Ahead by a Century: Discovery of Laves Phases Assisted by Machine Learning.

Laves phases AB2 form the most abundant group of intermetallic compounds, consisting of combinations of larger electropositive metals A with smaller metals B. Many practical applications of Laves phases depend on the ability to tune their physical properties through appropriate substitution of either the A or B component. Although simple geometrical and electronic factors have long been thought to control the formation of Laves phases, no single factor alone can make predictions accurately. Several machine learning models have been developed to discover new Laves phases, including variations caused by solid solubility, using elemental properties solely on the basis of chemical composition. These models were trained on a data set comprising about 3700 entries of experimentally known phases AB2 with Laves and non-Laves structures. Among these models, a decision tree algorithm gave very good performance (average recall of 95%, precision of 94%, and accuracy of 96% on the test set) by using only a small set of descriptors, the most important of which relates to the electron density at the boundary of the Wigner-Seitz cell for the B component. This model provides guidance for new experiments by making predictions on >400000 candidates very quickly. A chemically unintuitive candidate Cd(Cu1-xSbx)2 with a limited solid solubility of Sb for Cu was targeted; it was successfully synthesized and confirmed to adopt a cubic MgCu2-type Laves structure.

Role of Partial Vacancy and Structural Distortion in the Stability of Nonstoichiometric Phases Ni7-δInSe2-xSx (1.26 ≥ δ ≥ 0.94; 0 ≤ x ≤ 1.33).

This study explores the structure and stability of partly disordered sulfur-substituted Ni5.74InSe2 (I4/mmm, a = 3.6766(1) Å, c = 18.8178(10) Å, Z = 2). The structure of Ni7-δInSe2-xSx (x = 0.2, 0.36, 0.66, 0.80, 0.94) compounds is isotypic to their parent Ni5.74InSe2 and can be viewed as alternating heterometallic Cu3Au-type ∞2[Ni3In] slabs and defective Cu2Sb-type ∞2[Ni4-δ(Se/S)2] slabs along the [001]-axis. Similar to the parent Se-compound, the Ni-Ch (Ch = chalcogen) fragment is non-stoichiometric and possesses a partially occupied Ni-site. It was observed that with sulfur insertion at the selenium site of Ni5.74InSe2, the interatomic distance between the partially occupied nickel and mixed (S/Se) sites decreases from ∼2.24 to ∼1.95 Å, and the occupancy of the disordered nickel site simultaneously increases. The limiting composition Ni6.06InSe0.67S1.33 (x = 1.33, δ = 0.94) is formed in the sulfur-rich region. Its average structure resembles the Ni6SnS2-type and has a similar motif to Ni5.74InSe2; the only difference is that Cu3Au-type ∞2[Ni3In] alternates with two types of Ni-Ch fragments (Cu2Sb or Li2O type units). By using first-principles electronic structure calculations, we explained the presence of partially disordered nickel sites in the Ni-Ch fragment and rationalized why the nickel site occupancy increases with sulfur insertion.

Ni3InSb: Synthesis, Crystal Structure, Electronic Structure, and Magnetic Properties.

The ternary phase with the composition Ni3InSb has been synthesized by high-temperature synthesis and structurally characterized by a combination of X-ray analysis, neutron diffraction analysis, and theoretical calculations. The structure of Ni3InSb crystallizes in the orthorhombic space group Pnma with lattice constants a = 7.111(3) Å, b = 5.193(3) Å, and c = 8.2113(2) Å. The crystal structure contains ∼20 atoms in its unit cell, which are distributed over four crystallographically independent positions (two Ni, one In, and one Sb). The crystal structure can be considered as a ternary substitutional variant of Ni3Sn2 (Pnma, no. 62), where a trivalent In and a pentavalent Sb orderly occupy two tetravalent Sn sites of Ni3Sn2. This site decoration pattern of two neighboring elements, In and Sb, is unique and confirmed by first principles total energy calculations. The crystal structure can be described by two building units: Ni2Sb (building unit of Ni2In) and NiIn (NiAs-type). They alternate in the crystal structure and form infinite ac-slabs (puckered), and the slabs are stacked along [010]. A triangular lattice formed by Ni atoms indicates the existence of a geometrically frustrated structure. The calculated density of states and crystal orbital Hamilton population enlighten the stability and bonding characteristics of the structure. The temperature-dependent neutron diffraction study down to 5 K reveals that the crystal structure remains in the same orthorhombic symmetry with a weak anomaly in the lattice parameters at ∼100 K. Detailed temperature- and magnetic field-dependent magnetic properties of the title phase Ni3InSb show spin-glass- or spin-disorder-like behaviors below ∼300 K with an unusual magnetic behavior below 100 K, where an enhancement of magnetization with a decrease of the coercive field has been found.

Cu4TiTe4: Synthesis, Crystal Structure, and Chemical Bonding.

A new compound Cu4TiTe4 in the Cu-Ti-Te ternary system is prepared using high-temperature solid-state synthesis and characterized by single-crystal X-ray diffraction and energy-dispersive X-ray spectroscopy. The average structure of Cu4TiTe4 crystallizes in the cubic space group P4̅3m (cP9; a = 5.9484(1) Å) and adopts the Cu4TiSe4 structure type. Like Cu4TiSe4, it shows positional disorder in one of the two Cu sites. The three-dimensional structure of Cu4TiTe4 is viewed as a cubic close-packed (ccp) array of Te, where half of the tetrahedral holes are orderly occupied by three Cu and one Ti and the disordered Cu atoms effectively occupied 1/4 of the octahedral holes. The calculated density of states (DOS) discerns that the compound is a narrow-bandgap semiconductor, and the crystal orbital Hamilton population (COHP) analysis shows that though the individual Cu-Te short contact is relatively weak compared to the Ti-Te contact, Cu-Te bonds largely contribute toward the overall stability. Due to the unique atomic arrangements, some Te atoms in the unit cell have unsaturated coordination, which presents 5s2 lone pairs on the Te atoms. This has been confirmed by the density of states (DOS) and electron localization function (ELF) calculations.

Structure and Spin-Glass Magnetism of the MnxNi2Zn11-x Pseudobinary γ-Brasses at Low Mn Contents.

The pseudobinary MnxNi2Zn11-x γ-brass-type phases at low Mn dopant levels (x = 0.1-0.5) were investigated. Crystal structures were determined for the two loading compositions of x = 0.3 and 0.5. The structures were solved in the cubic space group of I43m and are described in close analogy to the Ni2Zn11 parent γ-brass that is based on the 26-atom cluster, consisting of inner tetrahedron (IT), outer tetrahedron (OT), octahedron (OH), and cuboctahedron (CO). The refined site occupancies of the MnxNi2Zn11-x (x = 0.3, 0.5) reveal that the cluster center, which is empty in the Ni2Zn11, shows a partial occupation by Zn, with a partial depletion of Zn at the IT sites. The OH sites show a mixed Zn/Mn occupation. The OT and CO sites remain intact with respect to Ni2Zn11. Magnetic properties were studied for the Mn0.3Ni2Zn10.7 composition. The temperature-dependent zero-field-cooled and field-cooled magnetization, the ac susceptibility, the M(H) hysteresis curves, the thermoremanent magnetization, and the memory effect demonstrate typical broken-ergodicity phenomena of a magnetically frustrated spin system below the spin freezing temperature Tf ≈ 16 K. The Mn0.3Ni2Zn10.7 γ-brass phase classifies as a spin glass, originating predominantly from the random distribution of diluted Mn moments on the octahedral partial structure.

Crystal structures of two very similar 2†×†2†×†2 superstructures of γ-brass-related phases in ternary Ir-Cd-Cu system.

A binary phase Ir8Cd41 in the Ir-Cd binary system and novel ternary phases in the Ir-Cd-Cu system have been synthesized from the constituent elements using high-temperature solid-state synthesis. The structure of previously reported Ir8Cd41 and newly found ternary phases in the Ir-Cd-Cu system have been characterized by single crystal X-ray diffraction and EDS analysis. The structural analysis reveals that Ir8Cd41 adopts V8Ga41-type structure and ternary Ir-Cd-Cu phases adopt two 2 × 2 × 2-superstructures of the γ-brass-related phase. The structures of ternary Ir-Cd-Cu phases are associated with structural disorder (vacancies as well as mixed site occupancies). The crystal structures of the ternary phases are viewed using layer description and cluster concept. The 2 × 2 × 2-superstructure of γ-brass-related phases in the Cu-poor region are not isostructural with the phases in the Cu-rich region, and they are consistent with the absence of a continuous phase region between two 2 × 2 × 2-superstructures of γ-brass-related phases. In the Cu-poor region, the structures contain ∼404 atoms per unit cell, whereas in the Cu-rich phases the structures contain ∼411 atoms in their respective unit cells. The crystal structures in the Cu-poor region represent a new type in the 2 × 2 × 2-superstructure of γ-brass-related phases in view of the combination of constituent cluster types, whereas the structures in the Cu-rich region adopt the Rh7Mg44 structure type.