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MnCoGe-based materials have the potential to exhibit giant magnetocaloric effects due to the coupling between magnetic ordering and a martensitic phase transition. Such coupling can be realized by ...

A series of solid solutions, CuFe

A new ternary selenide, Na2Mn3Se4, was prepared by a stoichiometric reaction between Na2Se4 and metallic Mn at 923 K. Crystal structure determination revealed a new structure type, built of alternating layers of Na+ ions and [Mn3Se4]2- anionic slabs. Band structure calculations indicate that Na2Mn3Se4 is an indirect band gap semiconductor with Eg = 1.59 eV, although a direct band gap is only marginally larger, at 1.64 eV. The material shows antiferromagnetic (AFM) ordering at 27 K, while the Weiss constant of ∼-400 K suggests much stronger nearest-neighbor AFM exchange between the Mn sites. This discrepancy is attributed to the strong spin frustration caused by a triangulated arrangement of the Mn sites in the [Mn3Se4]2- layer. The magnetic frustration leads to the stabilization of a complex AFM ordered structure with non-collinear arrangement of the Mn magnetic moments, as established from neutron diffraction data.

X-ray absorption spectroscopy (XAS) was used to elucidate changes in the electronic structure caused by the pressure-induced structural collapse in EuCo2 P2 . The spectral changes observed at the L3 -edge of Eu and K-edges of Co and P suggest electron density redistribution, which contradicts the formal charges calculated from the commonly used Zintl-Klemm concept. Quantum-chemical calculations show that, despite the increase in the oxidation state of Eu and the formation of a weak P-P bond in the high-pressure phase, the electron transfer from the Eu 4f orbitals to the hybridized 5d and 6s states causes strengthening of the Eu-P and P-P bonds. These changes explain the increased electron density on P atoms, deduced from the P K-edge XAS spectra. This work shows that the formal electron counting schemes do not provide an adequate description of changes associated with phase transitions in metallic systems with substantial mixing of the electronic states.

Using the experimental capability of the x-ray diffraction instrument available at the 25-T Florida split coil magnet at the NHMFL, we investigated the magnetostriction of polycrystalline $\mathrm{Al}{\mathrm{Fe}}_{2}{\mathrm{B}}_{2}$. The magnetostriction was measured in the vicinity of the ferromagnetic transition with ${T}_{C}=280\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, at 250, 290, and 300 K. $\mathrm{Al}{\mathrm{Fe}}_{2}{\mathrm{B}}_{2}$ exhibits an anisotropic change in lattice parameters as a function of magnetic field near the Curie temperature, and a monotonic variation as a function of applied field has been observed, i.e., the $c$ axis increases significantly while the $a$ and $b$ axes decrease with increasing field in the vicinity of ${T}_{C}$, irrespective of the measurement temperature. The volume magnetostriction decreases with decreasing temperature and changes its sign across ${T}_{C}$. Density functional theory calculations for the nonpolarized and spin-polarized (ferromagnetic) models confirm that the observed changes in lattice parameters due to spin polarization are consistent with the experiment. The relationships for magnetostriction are estimated based on a simplified Landau model that agrees well with the experimental results.

$\mathrm{L}{\mathrm{a}}_{0.4}\mathrm{C}{\mathrm{e}}_{0.6}\mathrm{C}{\mathrm{o}}_{2}{\mathrm{P}}_{2}$ represents a borderline case in the range of solid solutions formed in the pseudobinary system $\mathrm{LaC}{\mathrm{o}}_{2}{\mathrm{P}}_{2}\text{\ensuremath{-}}\mathrm{CeC}{\mathrm{o}}_{2}{\mathrm{P}}_{2}$. The material undergoes ferromagnetic ordering at \ensuremath{\sim}225 K followed by a structural collapse at \ensuremath{\sim}190 K, which leads to a strong suppression of magnetization. The structural phase transition manifests itself in a gradual decrease in the parameter $c$ and a relatively smaller increase of the parameter $a$ of the tetragonal lattice. Interestingly, a combination of magnetic measurements and nonpolarized and polarized neutron scattering experiments suggests that the structural collapse does not lead to an antiferromagnetically ordered state, observed in samples with the higher Ce content. On the contrary, $\mathrm{L}{\mathrm{a}}_{0.4}\mathrm{C}{\mathrm{e}}_{0.6}\mathrm{C}{\mathrm{o}}_{2}{\mathrm{P}}_{2}$ appears to enter a disordered, spin glass state, with gradual dissipation of the ferromagnetic ordering taking place simultaneously with the structural collapse, as evidenced by temperature-dependent measurements of the depolarization factor for a polarized neutron beam passing through the sample. The observed behavior is analogous to that reported for so-called reentrant spin glasses. In the present case, however, the appearance of the reentrant spin glass regime is caused not by tuning the chemical composition but by the structural phase transition. Electronic structure calculations confirm that the loss of magnetic ordering is caused by the subtle change to the density of states at the Fermi level due to the variation of the crystal structure of the material.

The crystal structure and magnetic properties of Cu0.6Mn2.4Ge2 have been re-investigated by a combination of extensive magnetic measurements and neutron scattering experiments, aided by electronic structure calculations. The material is found to be a soft ferromagnet with the ordering temperature TC = 316 K. The magnetocaloric effect evaluated from field-dependent magnetization isotherms is equal to 1.2 J/(kg·K) and 2.5 J/(kg·K) under the maximum applied magnetic field of 2 T and 5 T, respectively. The compound crystallizes in the hexagonal space group P63/mmc. A complex structural disorder necessitated testing of several disorder models against the results of non-polarized and polarized neutron scattering experiments and magnetization measurements. Simulations at the density-functional theory level were also performed to identify the most robust solution that properly described the data observed. The final magnetic structure model reveals non-equal magnetic moments on the Mn1 and Mn2 atoms (2.29(9) µB and 2.7(1) µB, respectively) and the presence of vacancies and minor Cu substitution defects in both Mn sites. The work demonstrates how the non-polarized and polarized neutron scattering methods can be combined with electronic structure calculations to establish the microscopic structure of magnetic materials with complex crystallographic disorder.

A new ternary selenide, Na

X-ray absorption spectroscopy (XAS) was used to elucidate changes in the electronic structure caused by the pressure-induced structural collapse in EuCo

Chalcogenide semiconducting nanoparticles are promising building blocks for solution-processed fabrication of optoelectronic devices. In this work, we report a new large-scale colloidal synthesis of metastable CuInSe2 nanoparticles with hexagonal plate-like morphology. Powder X-ray diffraction analysis of the nanoparticles showed that the structure of the nanoparticles is not simple hexagonal wurtzite-type CuInSe2 (space group P63mc), indicating the formation of an ordered superstructure. Detailed insight into this structural aspect was explored by high-resolution electron microscopy, and the results evidence an unreported chemical ordering within the synthesized CuInSe2 nanoparticles. Specifically, while the Se sublattice is arranged in perfect wurtzite subcell, Cu and In are segregated over distinct framework positions, forming domains with lower symmetry. The arrangement of these domains within the hexagonal Se substructure proceeds through the formation of a number of planar defects, mainly twins and antiphase boundaries. As a semiconductor, the synthesized material exhibits a direct optical transition at 0.95 eV, which correlates well with its electronic structure assessed by density functional theory calculations. Overall, these findings may inspire the design and synthesis of other nanoparticles featuring unique chemical ordering; thus, providing an additional possibility of tuning intrinsic transport properties., This work was supported by ERDF COMPETE 2020 and Portuguese FCT funds under the PrintPV project (PTDC/CTM-ENE/5387/2014, Grant Agreement No. 016663). B.F.G. is grateful to the FCT for the SFRH/BD/121780/2016 grant, while Y.V.K. is grateful to Portuguese NORTE 2020 programme (FROnTHERA project, NORTE-01-0145- FEDER-000023) for support of this research.

For a square matrix A, let S ( A ) be an eigenvalue inclusion set such as the Gershgorin region, the union of Cassini ovals, and the Ostrowski’s set. Characterization is obtained for maps Φ on n × n matrices satisfying S ( Φ ( A ) Φ ( B ) ) = S ( AB ) for all matrices A and B.

We report excellent electrocatalytic performance by AlFe2B2 in the oxygen-evolution reaction (OER). The inexpensive catalytic material, prepared simply by arc-melting followed by ball-milling, exhibits high stability and sustained catalytic performance under alkaline conditions. The overpotential value of 0.24 V observed at the current density of 10 mA cm−2 remained constant for at least 10 days. Electron microscopy and electron energy loss spectroscopy performed on the initial ball-milled material and on the material activated under electrocatalytic conditions suggest that the catalytic mechanism involves partial leaching of Al from the layered structure of AlFe2B2 and the formation of Fe3O4 nanoclusters on the exposed [Fe2B2] layers. Thus, the AlFe2B2 structure serves as a robust supporting material and, more importantly, as a pre-catalyst to the in situ formed active electrocatalytic sites. Comparative electrochemical measurements demonstrate that the electrocatalytic performance of the AlFe2B2-supported Fe3O4 nanoclusters substantially exceeds the results obtained with unsupported nanoparticles of Fe3O4, FeB, or such benchmark OER catalysts as IrO2 or RuO2. The excellent catalytic performance and long-term stability of this system suggests that AlFe2B2 can serve as a promising and inexpensive OER electrocatalyst Petroleum Research Fund of the American Chemical Society | Ref. 59251-ND10 U.S. National Science Foundation | Ref. DMR-1507233 European Commission | Ref. H2020, n. 686053 European Commission | Ref. NORTE-01-0145-FEDER-000023 Agence Nationale de la Recherche | Ref. ANR11-EQPX-0020

The interplay between the algebraic and analytic properties of a matrix and the geometric properties of its pseudospectrum is investigated. It is shown that one can characterize Hermitian matrices, positive semi-definite matrices, orthogonal projections, unitary matrices, etc. in terms of the pseudospectrum. Also, characterizations are given to maps on matrices leaving invariant the pseudospectrum of the sum, difference, or product of matrix pairs. It is shown that such a map is always a unitary similarity transform followed by some simple operations such as adding a constant matrix, taking the matrix transpose, or multiplying by a scalar in {1,-1}.