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Cs2Cu3(SeO3)4·2H2O is a ferrimagnet and exhibits a highly anisotropic 1/3-magnetization plateau. The necessary requirements for observing magnetic plateaus were explored by analyzing the topology of magnetic bonding.

We report on the magneto-structural properties of the rare copper aluminum hydroxo-arsenate mineral liroconite with chemical composition Cu2AlAs1−x P x O4(OH)4·4H2O (x ≈ 0.2). In order to characterize the natural mineral sample chemical analyses, X-ray single crystal and powder diffraction, heat capacity and crystal water desorption, anisotropic thermal expansion and Raman scattering and magnetic susceptibility investigations have been carried out. The magnetic properties are well described by two discrete oxygen bridged Cu2+ spin S = 1/2 dimers with antiferromagnetic spin exchange ranging between −320 K and −136 K, depending on to which group-15 five-valent cation, As5+ or P5+, the dimer bridging oxygen atoms coordinate to. Accordingly the temperature dependence of the magnetic susceptibilities can be well fitted to a sum of two Bleaney–Bowers type spin S = 1/2 dimer susceptibilities suggesting that the dimers show negligible mixed coordination to (AsO4)3−/(PO4)3− tetrahedra. DFT + U calculation confirm the ratio of the spin exchange parameters of the (AsO4)3− or (PO4)3− coordinated Cu2+ – Cu2+ dimers. Inter dimer spin exchange is about two orders of magnitude smaller than intra dimer exchange.

Mixed-valent Ba2Mn2+Mn23+(SeO3)6 crystallizes in a monoclinic P21/c structure and has honeycomb layers of Mn3+ ions alternating with triangular layers of Mn2+ ions. We established the key parameters governing its magnetic structure by magnetization M and specific heat Cp measurements. The title compound exhibits a close succession of a short-range correlation order at Tcorr = 10.1 ± 0.1 K and a long-range Néel order at TN = 5.7 ± 0.1 K, and exhibits a metamagnetic phase transition at T < TN with hysteresis most pronounced at low temperatures. The causes for these observations were found using the spin exchange parameters evaluated by density functional theory calculations. The title compound represents a unique case in which uniform chains of integer spin Mn3+ (S = 2) ions interact with those of half-integer spin Mn2+ (S = 5/2) ions.

The good thermal stability of a phosphor is crucial for its practical applications. Unfortunately, in the past decades, only the Gurney–Mott equation was available to describe the relation between the luminescence properties of a phosphor and temperature, which is, however, phenomenological and not precise. In this work, we introduced a hypothesis that the lowering of the luminescence efficiency of a phosphor is caused by the heat generated during the luminescence process and can be reduced if the luminescence site dissipates the heat away. We verified this hypothesis by evaluating the thermal conductivities κ of their luminescence sites, the Eu atoms, in the three phosphors, SrLiAl3N4:Eu2+, Sr2Si5N8:Eu2+ and SrSiN2:Eu2+, as well as those of the Sr atoms in their hosts SrLiAl3N4, Sr2Si5N8 and SrSiN2. It is suggested that our new approach can be employed as a practical criterion to search for phosphor materials with efficient luminescence properties.

Noncentrosymmetric hybrid framework (HF) materials are an important system in discovering new practical second-order nonlinear optical materials. We calculated the second harmonic generation (SHG) response of a noncentrosymmetric (NCS) organic–inorganic HF compound, CuMoO3(p2c) (p2c = pyrazine-2-carboxylate) to find that it exhibits the largest SHG response among all known NCS HF materials with one-dimensional helical chains. Further atom response theory analysis revealed that the metal atoms Cu and Mo contribute much more strongly than do nonmetal atoms in determining the strength of the SHG response, which is a novel example in nonlinear optical materials known to date.

Sr

Magnetic topological insulators (TIs), including the quantum anomalous Hall effect and antiferromagnetic TIs, have attracted significant attention owing to the exotic properties they give rise to, however, ferromagnetic TIs with gapless surface/edge states and a nonzero topological invariant have not been reported so far. Here, we show that a ferromagnetic topological insulating phenomenon is possible in a single layer honeycomb lattice on the basis of perturbation theory and model Hamiltonian analyses. As a probable candidate for the experimental realization of this phenomenon, we propose a hypothetical single-layer Na2MnPb with supporting evidence based on first-principles calculations. The topological nature of the single-layer Na2MnPb is confirmed by calculating the Wannier charge center, the spin Chern number, and the gapless edge states.

In implementing the materials genome approach to search for new materials with interesting properties or functions, it is necessary to find the correct functional motif. To this end, it is common to partition an extended structure into various building units and then partition its properties to find the appropriate functional motif. We have developed the general principles for partitioning a structure and its properties in terms of a set of atoms and bonds by analyzing the differential cross-sections of neutron and X-ray scattering phenomena and proposed the procedures with which to partition an extended structure and its properties. We demonstrate how these procedures work by analyzing the nonlinear optical crystal KBe2BO3F2. Our partitioning analysis of KBe2BO3F2 leads to the conclusion that the second harmonic generation response of KBe2BO3F2 is dominated by the ionically bonded metal-centered groups.

Two seemingly puzzling observations on two magnetic systems were analyzed. For the oxide-hydrides Sr2VO3H, Sr3V2O5H2, and SrVO2H, made up of VO4H2 octahedra, the spin orientations of the V3+ (d2, S = 1) ions were reported to be different, namely, perpendicular to the H-V-H bond in Sr2VO3H but parallel to the H-V-H bond in Sr3V2O5H2 and SrVO2H, despite that the d-state split patterns of the VO4H2 octahedra are similar in the three oxide-hydrides. Another puzzling observation is the contrasting magnetic structures of Sr2CoO2Cu2Te2 and Sr2MnO2Cu1.58Te2, consisting of the layers made up of corner-sharing MO4Te2 (M = Co, Mn) octahedra. The Co2+ spins in each CoO2Te2 layer are antiferromagnetically coupled with spins perpendicular to the Te–Co–Te bond, whereas the Mn3+/Mn2+ ions of each MnO2Te2 layer are ferromagnetically coupled with spins parallel to the Te-Mn-Te bonds. We investigated the cause for these observations by performing first-principles density functional theory (DFT) calculations for stoichiometr...

UiO-67 is a Zr-based metal–organic framework (MOF) containing an organic linker namely, the dianion of biphenyl-4,4′-dicarboxylic acid (bpdc). Ce4+ metal ions (0.02 Ce to Zr atom ratio) were incorporated into UiO-67 via partially replacing bpdc with the dianion of 2,2′-bipyridine-5,5′-dicarboxylic acid (bpydc); thus, the latter forms a bpydc-Ce complex. The resulting product (i.e., UiO-67-Ce) demonstrated a photocatalytic hydrogen evolution rate that was over 10 times higher than that of UiO-67. Through this modification, a new energy transfer channel is opened up. The energy transfer between the bpdc and bpydc-Ce ligands (i.e., from excited bpdc to bpydc-Ce) weakened the recombination of the charge carriers, which was confirmed by photoluminescence, emission lifetime, and transient absorption measurements. This study presents a new way to construct highly efficient MOF photocatalysts.

Magnetic ions M in discrete molecules and extended solids form MLn complexes with their first-coordinate ligand atoms L. The spin moment of M in a complex MLn prefers a certain direction in coordin...

A simple and efficient light-assisted method is employed to prepare powder samples of all-inorganic mixed-perovskite CsPbBr3-xIx from CsPbBr3 by ion exchange in aqueous HBr/KI solution such that the concentration of I in a sample particle decreases on going from the surface to the interior. CsPbBr3-xIx/Pt, namely, CsPbBr3-xIx samples loaded with Pt nanoparticles, shows a high performance for the hydrogen evolution under visible-light irradiation in aqueous HBr solution saturated with CsPbBr3. The H2 evolution rate of the CsPbBr3-xIx/Pt powders (200 mg) is determined to be 224 μmol h−1, under 120 mW cm-2 visible-light (λ ≥ 420 nm) illumination. The CsPbBr3-xIx samples have a high stability, with no apparent decrease in the catalytic activity after 50 h of repeated H2 evolution experiments. The apparent quantum efficiency of CsPbBr3-xIx/Pt is determined to be 2.15% under the irradiation of 450 nm light.

Neutron diffraction studies on magnetic solids composed of axially elongated CoO

The incommensurate magnetic structure (0.47, 0, 0.49) of NaYNiWO

Though titanium-based metal-organic frameworks (MOFs) are declared to be relatively water stable, their framework gradually collapses in water within days due to the attack of OH− to O Ti O bond. For practical applications of titanium-based MOFs, it is crucial to solve their instability problem in water. We searched for a simple and efficient method to enhance the stability of titanium-based MOFs in water by using Ti-ATA (ATA = 2-aminoterephthallate ion) as a representative titanium-based MOF. Here, we show that the stability of Ti-ATA in water is greatly improved nearly without affecting its porosity and photocatalytic activity by treating it with aqueous solutions containing metal ions of empty d orbitals (Y3+, La3+, Ce3+, Nd3+ and Tm3+) or partially-filled d orbitals (Cr3+).

The second harmonic generation (SHG) responses of the paraelectric and ferroelectric phases of KH

NiV-LDH as a novel electrode material has rarely been investigated in the energy storage field. Herein, novel ultrathin NiV-LDH was designed and synthesized, which displays high specific capacitance but poor stability. To further improve the stability, NiV-LDH was transformed to the sulfide named NiV-S through an ion exchange reaction (S2− replaces OH−). The obtained NiV-S maintains the ultrathin (5 nm in thickness) and porous structure, and displays higher specific capacitance (2270.4 F g−1 at 2 A g−1), compared to NiV-LDH (1502 F g−1 at 2 A g−1). What is more improtant is that the cycling stability of NiV-S is much higher than NiV-LDH, (91.9% retention after 10,000 cycles for NiV-S vs only 63% retention after 5000 cycles for NiV-LDH). The asymmetric supercapacitor assembled using ultrathin porous NiV-S as the positive electrode and activated carbon (AC) as the negative electrode was found to deliver a maximum energy density of 51 W h kg−1 at a power density of 1600 W kg−1 and 12 kW kg−1 at 23.7 W h kg−1. In addition, 98.5% of the initial capacitance retains after 10,000 continuous cycling.

To remedy the instability problem of the non-elemental-metal (NEM) plasmonic photocatalyst WO3−x in aqueous solution, a novel strategy of photoinduced electron injection was applied to construct CdS/WO3−x hetereostructures by growing WO3−x on semiconductor CdS nanowires. Under visible/near-infrared light irradiation, the NEM plasmonic CdS/WO3−x nanowires are highly stable and exhibit a much higher activity (1.60 mmol g−1 h−1) than do plasmonic WO3−x (negligible amount) and semiconductor CdS (0.53 mmol g−1 h−1) in hydrogen generation. Wavelength dependent photocatalytic performance and Single-particle PL study demonstrate that photo-excited electrons on CdS continually inject into conduction band of WO3−x, so that the surface plasmon resonance (SPR) of the NEM plasmonic photocatalyst WO3−x is sustained while hot electrons generated by the SPR excitation are consumed for hydrogen generation.

We examined how to enhance the lifetime of organic light-emitting diodes (OLEDs) based on bipolar host molecules ET-HT, where ET and HT refer to electron- and hole-transporting units, respectively, by analyzing their thermodynamic and kinetic stabilities. Our DFT calculations reveal that the thermodynamic stability of ET-HT is determined by that of its anion, which is difficult to improve by chemical modifications of ET and HT. The kinetic stability of ET-HT can be enhanced by the spiroconjugation between ET and HT, which occurs when their π-frameworks are extended and have an orthogonal arrangement. Green OLED devices were fabricated by using ET-HTs with and without spiroconjugation, to find that the device with spiroconjugation has a lifetime that is approximately 6 times longer than the one without spiroconjugation.

The removal of nonpolar gaseous ethylene molecules on the plasmonic photocatalyst Ag/AgCl/TiO2 was examined under simulated sunlight irradiation, to find that it has a markedly high activity for the oxidation of ethylene molecules. Systematic experiments, carried out to probe the cause for this observation, indicate that the strong electric field mainly on the Ag nanoparticles (NPs) generated by their surface plasmon resonance (SPR) induces polarization in gaseous ethylene molecules hence enhancing their adsorption on the catalysts and their subsequent photodegradation, and that TiO2 acts as a substrate for dispersing Ag/AgCl nanoparticles to have a larger active surface area. This study provides new ideas towards designing advanced photocatalysts for the degradation of nonpolar gaseous molecules.

The solid state phase diagram for the equilibria of the ternary Ta-Ti-P system was established by X-ray powder diffraction at T = 1070 K in the region up to 67 at.% P. Isostructural compounds Ta3P and Ti3P (both Ti3P-type) form a continuous series of substitution-type solid solutions. The majority of binary compounds form substitution-type solid solutions, in which the substitution of Ti for Ta, or Ta for Ti, takes place. The crystal structure investigation of the new ternary phosphide demonstrates that this phase is isotypical to the OsGe2 structure type and has a small homogeneity range, which can be described by the formula Та1-xТіxР2 (x = 0.07(3)−0.145(7), space group C2/m, a = 8.8556(9)−8.8446(2), b = 3.2654(4)−3.2605(1), c = 7.4846(8)−7.4741(1) A, β = 119.307(2)−119.308(1)°). Our density functional theory (DFT) electronic structure calculations show that the stoichiometric composition TaP2 has no electronic instability, although it does not exist under the thermal conditions used in present study. The addition of a small amount of Ti leads to a ternary phase Та1-xТіxР2 (x = 0.07(3)−0.145(7)) with a higher thermal stability compared to TaP2.

The read/write operations with individual quantum bits (i.e., qbits) is a challenging problem to solve in quantum computing. To alleviate this difficulty, we considered the possibility of using a group of qbits that act collectively as a bit (hereafter, a group bit or a gbit, in short). A promising candidate for a gbit is a single-domain ferromagnet (SDF) independent of its size, which can be prepared as a magnet of well separated uniaxial magnetic ions (UMIs) at sites of no electric dipole moment with their uniaxial axes aligned along one common direction. When magnetized, the UMIs of such a magnet have a ferromagnetic (FM) arrangement and the resulting SDF becomes a gbit with its two opposite moment orientations representing the |0> and |1> states of a bit. We probed the requirements for such magnets, and identified several 2H-perovskites as materials satisfying these requirements.

When doped with oxygen, the layered Y2O2Bi phase becomes a superconductor. This finding raises questions about the sites for doped oxygen, the mechanism of superconductivity, and practical guidelines for discovering new superconductors. We probed these questions in terms of first-principles calculations for undoped and O-doped Y2O2Bi. The preferred sites for doped O atoms are the centers of Bi4 squares in the Bi square net. Several Bi 6p x/y bands of Y2O2Bi are raised in energy by oxygen doping because the 2p x/y orbitals of the doped oxygen make antibonding possible with the 6p x/y orbitals of surrounding Bi atoms. Consequently, the condition necessary for the “flat/steep” band model for superconductivity is satisfied in O-doped Y2O2Bi.

Hole-doped layered BiCuSeO phases include substitutionally doped Bi1–xAxCuSeO (A = alkali, alkaline earth) as well as vacancy-doped Bi1−δCu1-γSeO and Bi1−δCuSeO. To probe how their Seebeck coefficients are related to their hole density p, we calculated the Seebeck coefficient for defect-free BiCuSeO as a function of the hole density, which is generated by lowering the Fermi level from the valence band maximum (VBM). In addition, we calculated the Seebeck coefficient for Bi1−δCuSeO (δ = 1/32, 1/16) with a large number of Bi vacancies. The Seebeck coefficients of the hole-doped BiCuSeO phases are governed by the electronic states lying within ∼0.5 eV from the VBM. These states are composed of largely Cu 3d xz/yz and Se 4p x/y states and possess the character of a uniform one-dimensional (1D) chain rather than a uniform two-dimensional (2D) lattice expected for a layered phase. The observed S-vs-p relationship for Bi1–xAxCuSeO (A = alkali, alkaline earth) as well as Bi1−δCu1-γSeO (δ = 0, 0.025; γ = 0, 0.025)...

When its surface is modified by using polar organic anions, 4-substituted thiophenolate anions 4-Z-C6H4S− (Z = NO2, COOH, H, CH3, and NH2), the Bi-based semiconductor BiO(HCOO) was found to exhibit a greatly enhanced photocatalytic activity. To establish the generality of this phenomenon, we examined the photocatalytic activities of other Bi-based semiconductors, BiOX (X = Cl, Br, and I), (BiO)2CO3 and Bi2O3, by modifying their surfaces with 4-carboxythiophenolate anions (4CBTs). As observed for BiO(HCOO), it is found that the surface modification with the 4CBT anions enhances the photocatalytic activities of BiOX (X = Cl, Br, and I), (BiO)2CO3 and Bi2O3, and this enhancement originates from a synergetic effect between the polarity of the polar organic anions and the internal electric field of those Bi-based semiconductors. Several factors affecting the photocatalytic activity were probed in some detail, which includes the nature of the facets and the sample sizes modified by using 4CBT anions in BiOCl and (BiO)2CO3, the structures of Bi2O3 phases as well as the electron-withdrawing or electron-donating ability of the 4-substituent Z of 4-Z-C6H4S− in BiOX (X = Cl, Br, and I).

In developing physical theories, analogical reasoning has been found to be very powerful, as attested by a number of important historical examples. An analogy between two apparently different phenomena, once established, allows one to transfer information and bring new concepts from one phenomenon to the other. Here, we discuss an important analogy between two widely different physical problems, namely, the Jahn–Teller distortion in molecular physics and the Rashba spin splitting in condensed matter physics. By exploring their conceptual and mathematical features and by searching for the counterparts between them, we examine the orbital texture in Jahn–Teller systems, as the counterpart of the spin texture of the Rashba physics, and put forward a possible way of experimentally detecting the orbital texture. Finally, we discuss the analogy by comparing the coexistence of linear Rashba + Dresselhaus effects and Jahn–Teller problems for specific symmetries, which allow for nontrivial spin and orbital textures, respectively.

The cause for the orbital-ordered structure of orthorhombic Cs

Rare-earth indium oxides RInO

A nonpolar inorganic layered semiconductor becomes an efficient visible-light photocatalyst when its surface layer becomes polar by chemically attaching electron-withdrawing 4-substituted thiophenolates -S-C6H4Z (Z = NO2, COOH, Cl, Br, H, CH3, NH2) via Bi-S bonds. An in-depth study finds a correlation between the apparent rate constant (kapp) and the Hammett constants σpara of the 4-substituted groups.

For most chemists and physicists, electron spin is merely a means needed to satisfy the Pauli principle in electronic structure description. However, the absolute orientations of spins in coordinate space can be crucial in understanding the magnetic properties of materials with unpaired electrons. At low temperature, the spins of a magnetic solid may undergo long-range magnetic ordering, which allows one to determine the directions and magnitudes of spin moments by neutron diffraction refinements. The preferred spin orientation of a magnetic ion can be predicted on the basis of density functional theory (DFT) calculations including electron correlation and spin-orbit coupling (SOC). However, most chemists and physicists are unaware of how the observed and/or calculated spin orientations are related to the local electronic structures of the magnetic ions. This is true even for most crystallographers who determine the directions and magnitudes of spin moments because, for them, they are merely the parameters needed for the diffraction refinements. The objective of this article is to provide a conceptual framework of thinking about and predicting the preferred spin orientation of a magnetic ion by examining the relationship between the spin orientation and the local electronic structure of the ion. In general, a magnetic ion M (i.e., an ion possessing unpaired spins) in a solid or a molecule is surrounded with main-group ligand atoms L to form an MLn polyhedron, where n is typically 4-6, and the d states of MLn are split because the antibonding interactions of the metal d orbitals with the p orbitals of the surrounding ligands L depend on the symmetries of the orbitals involved.1 The magnetic ion M of MLn has a certain preferred spin direction because its split d states interact among themselves under SOC.2,3 The preferred spin direction can be readily predicted on the basis of perturbation theory in which the SOC is taken as perturbation and the split d states as unperturbed states by inspecting the magnetic quantum numbers of its d orbitals present in the HOMO and LUMO of the MLn polyhedron. This is quite analogous to how chemists predict whether a chemical reaction is symmetry-allowed or symmetry-forbidden in terms of the HOMO-LUMO interactions by simply inspecting the symmetries of the frontier orbitals.4,5 Experimentally, the determination of the preferred spin orientations of magnetic ions requires a sophisticated level of experiments, for example, neutron diffraction measurements for magnetic solids with an ordered spin state at a very low temperature. Theoretically, it requires an elaborate level of electronic structure calculations, namely, DFT calculations including electron correlation and SOC. We show that the outcomes of such intricate experimental measurements and theoretical calculations can be predicted by a simple perturbation theory analysis.

We examined the magnetic properties of layered oxide Li4NiTeO6 by magnetic susceptibility, magnetization and ESR measurements and density functional calculations, and characterized phase relations, crystal structure and electrochemical properties of Li4NiTeO6. The magnetization and ESR data indicate the absence of a long-range magnetic order down to 1.8 K, and the magnetic susceptibility data the presence of dominant antiferromagnetic interactions. These observations are well accounted for by density functional calculations, which show that the spin exchanges of the LiNiTeO6 layers in Li4NiTeO6 are strongly spin frustrated. The electrochemical charging of Li4NiTeO6 takes place at constant potential of ca. 4.2 V vs. Li/Li+ indicating two-phase process as confirmed by X-rays. The starting phase is only partially recovered on discharge due to side reactions.