Fermi surface and light quasi particles in hourglass nodal chain metalß-ReO2.

Quantum oscillations (QOs) in magnetic torque and electrical resistivity were measured to investigate the electronic structure ofß-ReO2, a candidate hourglass nodal chain (NC) metal (Dirac loop chain metal). All the de Haas-van Alphen oscillation branches measured at 30 mK in magnetic fields of up to 17.5 T were consistent with first-principles calculations predicting four Fermi surfaces (FSs). The small-electron FS of the four FSs exhibited a very small cyclotron mass, 0.059 times that of the free electrons, which is likely related to the linear dispersion of the energy band. The consistency between the QO results and band calculations indicates the presence of the hourglass NC predicted forß-ReO2in the vicinity of the Fermi energy.

Mechanism of Reductive Fluorination by PTFE-Decomposition Fluorocarbon Gases for WO3.

Reductive fluorination, which entails the substitution of O2- from oxide compounds with F- from fluoropolymers, is considered a practical approach for preparing transition-metal oxyfluorides. However, the current understanding of the fundamental reaction paths remains limited due to the analytical complexities posed by high-temperature reactions in glassware. Therefore, to expand this knowledgebase, this study investigates the reaction mechanisms behind the reductive fluorination of WO3 using polytetrafluoroethylene (PTFE) in an Ni reactor. Here, we explore varied reaction conditions (temperature, duration, and F/W ratio) to suppress the formation of carbon byproducts, minimize the dissipation of fluorine-containing tungsten (VI) compounds, and achieve a high fluorine content. The gas-solid reaction paths are analyzed using infrared spectroscopy, which revealed tetrafluoroethylene (C2F4), hexafluoropropene (C3F6), and iso-octafluoroisobutene (i-C4F8) to be the reactive components in the PTFE-decomposition gas during the reactions with WO3 at 500 °C. CO2 and CO are further identified as gaseous byproducts of the reaction evincing that the reaction is prompted by difluorocarbene (:CF2) formed after the cleavage of C═C bonds in i-C4F8, C3F6, and C2F4 upon contact with the WO3 surface. The solid-solid reaction path is established through a reaction between WO3 and WO3-xFx where solid-state diffusion of O2- and F- is discerned at 500 °C.

Antimicrobial surface processing of polymethyl methacrylate denture base resin using a novel silica-based coating technology.

OBJECTIVES: This study investigated the surface characteristics of denture base resin coatings prepared using a novel silica-based film containing hinokitiol and assessed the effect of this coating on Candida albicans adhesion and growth. METHODS: Silica-based coating solutions (control solution; CS) and CS containing hinokitiol (CS-H) were prepared. C. albicans biofilm formed on denture base specimens coated with each solution and these uncoated specimens (control) were analyzed using colony-forming unit (CFU) assay, fluorescence microscopy, and scanning electron microscopy (SEM). Specimen surfaces were analyzed by measuring the surface roughness and wettability and with Fourier-transform infrared (FT-IR) and proton nuclear magnetic resonance (1H NMR). Stability of coated specimens was assessed via immersion in water for 1 week for each group (control-1w, CS-1w, and CS-H-1w) followed by CFU assay, measurement of surface roughness and wettability, and FT-IR. RESULTS: CS-H and CS-H-1w contained significantly lower CFUs than those present in the control and control-1w, which was also confirmed via SEM. Fluorescence microscopy from the CS-H group identified several dead cells. The values of surface roughness from coating groups were significantly less than those from the control and control-1w. The surface wettability from all coating groups exhibited high hydrophobicity. FT-IR analyses demonstrated that specimens were successfully coated, and 1H NMR analyses showed that hinokitiol was incorporated inside CS-H. CONCLUSIONS: A silica-based denture coating that incorporates hinokitiol inhibits C. albicans growth on denture. CLINICAL RELEVANCE: We provide a novel antifungal denture coating which can be helpful for the treatment of denture stomatitis.

Successive phase transitions of the spin-orbit-coupled metal Cd2Re2O7probed by high-resolution synchrotron x-ray diffraction.

The 5dpyrochlore oxide superconductor Cd2Re2O7(CRO) has attracted significant interest as a spin-orbit-coupled metal (SOCM) that spontaneously undergoes a phase transition to an odd-parity multipole phase by breaking the spatial inversion symmetry due to the Fermi liquid instability caused by strong spin-orbit coupling. Despite the significance of structural information during the transition, previous experimental results regarding lattice deformation have been elusive. We have conducted ultra-high resolution synchrotron radiation x-ray diffraction experiments on a high-quality CRO single crystal. The temperature-dependent splitting of the 0 0 16 and 0 0 14 reflections, which are allowed and forbidden, respectively, in the high-temperature cubic phase I (space groupFd-3m), has been clearly observed and reveals the following significant facts: inversion symmetry breaking and tetragonal distortion occur simultaneously atTs1= 201.5(1) K; the previously believed first-order transition between phase II (I-4m2) and phase III (I4122) atTs2∼120 K consists of two close second-order transitions atTs2= 115.4(1) K andTs3∼ 100 K; there is a new orthorhombic phase XI (F222) in between. The order parameters (OPs) of these continuous transitions are uniquely represented by a two-dimensional irreducible representationEuof theOhpoint group, and the OPs of phase XI are a linear combination of those of phases II and III. Each phase is believed to correspond to a distinct odd-parity multipole order, and the complex successive transitions observed may be the result of an electronic phase transition that resolves the Fermi liquid instability in the SOCM.

Characterization of the charge transfer luminescence of the [WO6]6- octahedron in Ca3WO6 and the [WO5]4- square pyramid in Ca3WO5Cl2.

Charge transfer (CT) luminescence of different types of polyhedra, [WO5]4- in Ca3WO5Cl2 and [WO6]6- in Ca3WO6, is characterized by spectroscopic experiments and ab initio calculations. According to the geometry optimization, W6+ ions form five-fold [WO5]4- square pyramids in Ca3WO5Cl2 because of a large interatomic distance between W6+ and Cl- of 3.266 Å. The analysis of the density of electronic states reveals the ionic character of Cl- ions to the W6+ ions in the Ca3WO5Cl2 lattice, resulting in the observed broad luminescence band peak at 488 nm of the single-crystal Ca3WO5Cl2 sample being assigned to the CT transition in the [WO5]4- square pyramid. Compared with the [WO6]6- octahedron in Ca3WO6, the [WO5]4- square pyramid shows an inconsistent CT energy shift: higher CT absorption and lower luminescence energies. The larger bandgap brings about higher absorption energy due to the structural and compositional features of the orthorhombic Ca3WO5Cl2. The redshifted CT luminescence band and small activation energy for the thermal quenching of the Ca3WO5Cl2 sample are explained, assuming that the CT states of the anisotropic [WO5]4- square pyramid take a larger offset in the configurational coordinate diagram than the [WO6]6- octahedron.

Linear Trimer Molecule Formation by Three-Center-Four-Electron Bonding in a Crystalline Solid RuP.

Some inorganic solids undergo phase transitions that result in the formation of "molecules" in their crystalline frameworks, which are frequently accompanied by dramatic changes in physical properties; the metal-insulator transition (MIT) in vanadium dioxide, for instance, is accompanied by the formation of dimer molecules with conventional two-center-two-electron bonding. We have discovered the creation of a linear ruthenium trimer with atypical three-center-four-electron bonding in ruthenium monophosphide at its MIT. Our detailed structural investigation and electronic structure calculations reveal that charge transfer from polymerized phosphorous to ruthenium automatically tunes the electron density to precisely four per trimer at the MIT, with all conduction electrons present at high temperatures being trapped by the trimer's molecular orbitals at low temperatures. Our results demonstrate that molecules are essential even in solid crystals, as they impact their electronic properties.

Inorganic Structural Chemistry of Titanium Dioxide Polymorphs.

Apart from rutile, which crystallizes in the rutile-type structure characteristic of many metal dioxides, three major polymorphs of titanium dioxide (TiO2) are known: anatase, brookite, and the α-lead dioxide (α-PbO2)-type high-pressure form. Ti ions are commonly found in octahedra composed of six oxide ions, and their crystal structures are distinguished according to the linkage pattern of the TiO6 octahedra. Inorganic structural chemistry considers that, in the rutile and α-PbO2 types, Ti ions occupy half of the octahedral voids in the hexagonal close packing of oxide ions, and the TiO6 octahedra in each layer are joined via edge sharing to form linear and zigzag strands, respectively. Anatase and brookite, on the other hand, exhibit more complex three-dimensional edge-sharing octahedral connections, although their origins are not fully explained. I show that these configurations can be interpreted as distinct stacking structures of layers with α-PbO2-type zigzag strands. Additionally, I characterize the crystal structures of four TiO2 polymorphs in detail using stacking sequence descriptions based on anion close packings and explore their relationships in terms of inorganic structural chemistry. I note that the moderate covalent nature of the Ti-O bond and the local structural instability of d0 ions result in an unusual variety of polymorphs in TiO2.

Surface Functionalization of Non-Woven Fabrics Using a Novel Silica-Resin Coating Technology: Antiviral Treatment of Non-Woven Fabric Filters in Surgical Masks.

Masks are effective for preventing the spread of COVID-19 and other respiratory infections. If antimicrobial properties can be applied to the non-woven fabric filters in masks, they can become a more effective countermeasure against human-to-human and environmental infections. We investigated the possibilities of carrying antimicrobial agents on the fiber surfaces of non-woven fabric filters by applying silica-resin coating technology, which can form silica-resin layers on such fabrics at normal temperature and pressure. Scanning electron microscopy and electron probe microanalysis showed that a silica-resin layer was formed on the fiber surface of non-woven fabric filters. Bioassays for coronavirus and quantitative reverse transcription-polymerase chain reactions (RT-PCR) revealed that all antimicrobial agents tested loaded successfully onto non-woven fabric filters without losing their inactivation effects against the human coronavirus (inhibition efficacy: >99.999%). These results indicate that this technology could be used to load a functional substance onto a non-woven fabric filter by vitrifying its surface. Silica-resin coating technology also has the potential of becoming an important breakthrough not only in the prevention of infection but also in various fields, such as prevention of building aging, protection of various cultural properties, the realization of a plastic-free society, and prevention of environmental pollution.

High-Pressure Synthesis of Transition-Metal Oxyhydrides with Double-Perovskite Structures.

We report on the high-pressure synthesis, crystal structure, and magnetic properties of four novel transition-metal oxyhydrides─Ba2NaVO3H3, Ba2NaVO2.4H3.6, Ba2NaCrO2.2H3.8, and Ba2NaTiO3H3─crystallizing in the double-perovskite structure. Notably, they have a higher hydride content in their anion sites (50%-63%) than known oxyhydrides with perovskite structures do (≤33%). Vanadium and chromium oxyhydrides exhibited Curie-Weiss magnetic susceptibilities with no magnetic ordering down to 2 K, which may be due to geometrical frustration in their face-centered lattices and weak magnetic interactions. Density functional theory calculations revealed that the transition metal-hydride bonding nature of the prepared oxyhydrides is more covalent than that observed for known perovskite oxyhydrides, as evidenced by the shorter bond lengths of the former. Remarkably, our double-perovskite oxyhydrides with a high hydride content may possess a bonding character intermediate between those of known oxyhydrides and hydrides.

Pyrochlore oxide Hg2Os2O7on verge of metal-insulator boundary.

Semimetallic osmium pyrochlore oxide Cd2Os2O7undergoes a magnetic transition to an all-in-all-out (AIAO)-type order at 227 K, followed by a crossover to an AIAO insulator at around 210 K. Here, we studied the isostructural and isoelectronic compound Hg2Os2O7through thermodynamic measurements, muon spin rotation (µSR) spectroscopy and neutron diffraction experiments. A similar magnetic transition, probably to an AIAO-type order, was observed at 88 K, while the resistivity showed a decrease at the transition and remained metallic down to 2 K. Thus, the ground state of Hg2Os2O7is most likely an AIAO semimetal, which is analogous to the intermediate-temperature state of Cd2Os2O7. Hg2Os2O7exists on the verge of the metal-insulator boundary on the metal side and provides an excellent platform for studying the electronic instability of 5delectrons with moderate electron correlations and strong spin-orbit interactions.

Dimensional reduction by geometrical frustration in a cubic antiferromagnet composed of tetrahedral clusters.

Dimensionality is a critical factor in determining the properties of solids and is an apparent built-in character of the crystal structure. However, it can be an emergent and tunable property in geometrically frustrated spin systems. Here, we study the spin dynamics of the tetrahedral cluster antiferromagnet, pharmacosiderite, via muon spin resonance and neutron scattering. We find that the spin correlation exhibits a two-dimensional characteristic despite the isotropic connectivity of tetrahedral clusters made of spin 5/2 Fe3+ ions in the three-dimensional cubic crystal, which we ascribe to two-dimensionalisation by geometrical frustration based on spin wave calculations. Moreover, we suggest that even one-dimensionalisation occurs in the decoupled layers, generating low-energy and one-dimensional excitation modes, causing large spin fluctuation in the classical spin system. Pharmacosiderite facilitates studying the emergence of low-dimensionality and manipulating anisotropic responses arising from the dimensionality using an external magnetic field.

Possible quadrupole order in tetragonal Ba2CdReO6and chemical trend in the ground states of 5d1double perovskites.

The synthesis and physical properties of the double perovskite (DP) compound Ba2CdReO6with the 5d1electronic configuration are reported. Three successive phases originating from a spin-orbit-entangledJeff= 3/2 state, confirmed by a reduced effective magnetic moment of 0.72 µB, were observed upon cooling. X-ray diffraction measurements revealed a structural transition from a high-temperature cubic structure to a low-temperature tetragonal structure atTs= 170 K, below which theJeff= 3/2 state was preserved. Magnetization, heat capacity, and thermal expansion measurements showed two more electronic transitions to a possible quadrupole ordered state atTq= 25 K and an antiferromagnetic order of dipoles with a ferromagnetic moment of ∼0.2 µBatTm= 12 K. These properties were compared with those of the DP's sister compounds Ba2BReO6(B= Mg, Zn, and Ca) and the chemical trend is discussed in terms of the mean-field theory for spin-orbit-coupled 5delectrons (2010 Chenet al Phys. Rev. B82174440). The DP Ba2BReO6compounds provide a unique opportunity for a systematic investigation of symmetry breaking in the presence of multipolar degrees of freedom.

Anisotropic Triangular Lattice Realized in Rhenium Oxychlorides A3ReO5Cl2 (A = Ba, Sr).

We report the synthesis, crystal structure, and magnetic properties of the two new quantum antiferromagnets A3ReO5Cl2 (A = Sr, Ba). The crystal structure is isostructural with the mineral pinalite Pb3WO5Cl2, in which the Re6+ ion is square pyramidally coordinated by five oxide atoms and forms an anisotropic triangular lattice (ATL) made of S = 1/2 spins. The magnetic interactions J and J' in the ATL are estimated from magnetic susceptibilities to be 19.5 (44.9) and 9.2 (19.3) K, respectively, with J'/J = 0.47 (0.43) for A = Ba (Sr). For each compound, the heat capacity at low temperatures shows a large T-linear component with no signature of long-range magnetic order above 2 K, which suggests a gapless spin liquid state of one-dimensional character of the J chains in spite of the significantly large J' couplings. This is a consequence of one-dimensionalization by geometrical frustration in the ATL magnet; a similar phenomenon has been observed in two compounds with slightly smaller J'/J values: Cs2CuCl4 (J'/J = 0.3) and the related compound Ca3ReO5Cl2 (0.32). Our findings demonstrate that 5d mixed-anion compounds provide a unique opportunity to explore novel quantum magnetism.

Titanium Hydride Complex BaCa2Ti2H14 with 9-Fold Coordination.

We present the high-pressure synthesis and crystal structure of a novel titanium hydride complex, BaCa2Ti2H14, with 9-fold coordination. It comprises a unique dinuclear [Ti2H14]6- complex that consists of a pair of Ti4+ ions each coordinated by nine hydrides in the monocapped square antiprism, distinguished from the known 9-fold coordination in the mononuclear tricapped trigonal prism of [MH9]x-. The dinuclear hydride complex is stabilized by three-center two-electron bonding at the four bridging Ti-H-Ti bonds to compensate for the lack of valence electrons in the Ti4+ ions. Optical measurements show that BaCa2Ti2H14 is a band insulator with a wide band gap of 2.25 eV. Density functional theory calculations reveal that the top of the valence band is dominated by H-1s-derived states, as expected from the 9-fold coordination, which would present a playground for electronic properties such as high-Tc superconductivity when doped with hole carriers or under high pressure.

Thermal-transport studies of kagomé antiferromagnets.

Searching for the ground state of a kagomé Heisenberg antiferromagnet (KHA) has been one of the central issues of condensed-matter physics, because the KHA is expected to host spin-liquid phases with exotic elementary excitations. Here, we show our longitudinal ([Formula: see text]) and transverse ([Formula: see text]) thermal conductivities measurements of the two kagomé materials, volborthite and Ca kapellasite. Although magnetic orders appear at temperatures much lower than the antiferromagnetic energy scale in both materials, the nature of spin liquids can be captured above the transition temperatures. The temperature and field dependence of [Formula: see text] is analyzed by spin and phonon contributions, and large sample variations of the spin contribution are found in volborthite. Clear changes in [Formula: see text] are observed at the multiple magnetic transitions in volborthite, showing different magnetic thermal conduction in different magnetic structures. These magnetic contributions are not clearly observed in low-[Formula: see text] crystals of volborthite, and are almost absent in Ca kapellasite, showing the high sensitivity of the magnetic excitation in [Formula: see text] to the defects in crystals. On the other hand, a clear thermal Hall signal has been observed in the lowest-[Formula: see text] crystal of volborthite and in Ca kapellasite. Remarkably, both the temperature dependence and the magnitude of [Formula: see text] of volborthite are found to be very similar to those of Ca kapellasite, despite of about an order of magnitude difference in [Formula: see text] We find that [Formula: see text] of both compounds is well reproduced, both qualitatively and quantitatively, by spin excitations described by the Schwinger-boson mean-field theory applied to KHA with the Dzyaloshinskii-Moriya interaction. This excellent agreement demonstrates not only that the thermal Hall effect in these kagomé antiferromagnets is caused by spins in the spin liquid phase, but also that the elementary excitations of this spin liquid phase are well described by the bosonic spin excitations.

Na3Pt10Si5: A Non-Centrosymmetric Superconductor Having Rattling Na Atoms in the Tunnel Framework Structure.

Single crystals of a novel Na-Pt-Si ternary compound, Na3Pt10Si5, were synthesized by heating the constituent elements at 1423 K. It crystallizes in a non-centrosymmetric trigonal structure of space group R32 (Z = 3) with lattice constants of a = 10.1536(3) Å and c = 10.1539(3) Å at 300 K. The structure consists of a three-dimensional framework made of Pt and Si atoms, and the Na atoms are contained in the tunnels of the framework. The large magnitude and the temperature dependence of the atomic displacement parameter of the Na site reveal a large thermal vibration indicative of a "rattling" motion of Na atoms in the oversized tunnel. The electronic structure calculations explain the observed metallic properties on the basis of the covalent bonds between the Pt and Si atoms in the framework and the ionic bonding of the Na atoms to the framework. A type II superconductivity with a transition temperature of 2.9 K and an upper critical field of 2.5 kOe are observed for a polycrystalline sintered bulk sample of Na3Pt10Si5 prepared by heating at 1353 K in Na vapor. Heat capacity measurements reveal a strong coupling superconductivity that is probably caused by an electron-phonon interaction enhanced by the rattling motion of the Na atoms.

Orbital Transitions and Frustrated Magnetism in the Kagome-Type Copper Mineral Volborthite.

Volborthite Cu3V2O7(OH)2·2H2O is a copper mineral that materializes a two-dimensional quantum magnet comprising a kagome net of spin-1/2 Cu2+ ions. We prepared single crystals of volborthite using hydrothermal conditions and investigated their crystal structures and magnetic properties. Unusual orbital "switching" and "flipping" transitions were observed: in the former type of transition (switching), the Cu 3d orbital occupied by an unpaired electron changes between the d(3z2-r2) and d(x2-y2) types, and in the latter type of transition (flipping), the d(x2-y2)-type orbitals change their directions. Their origin is ascribed to variations in the orientation of water molecules in the gap between the kagome layers and the accompanying changes of hydrogen bonding. These orbital transitions dramatically modify the magnetic interactions between Cu2+ spins, from the anisotropic kagome type to the formation of spin trimers over the kagome net. The effective spin 1/2 generated on the trimers exhibits a frustrated magnetism, resulting in a rich phase diagram in the magnetic fields. Volborthite is a unique compound showing an exceptional interplay between the orbital and spin degrees of freedom.

Possible observation of quantum spin-nematic phase in a frustrated magnet.

Water freezes into ice in winter and evaporates into vapor in summer. Scientifically, the transformations between solid, liquid, and gas are called phase transitions and can be classified through the changes in symmetry which occur in each case. A fourth phase of matter was discovered late in the 19th century: the liquid crystal nematic, in which rod- or disk-shaped molecules align like the atoms in a solid, while continuing to flow like a liquid. Here we report thermodynamic evidence of a quantum analog of the classical nematic phase, the quantum spin nematic (SN). In an SN, the spins of a quantum magnet select a common axis, like a nematic liquid crystal, while escaping conventional magnetic order. Our state-of-the-art thermal measurements in high pulsed magnetic fields up to 33 T on the copper mineral volborthite with spin 1/2 on a frustrated lattice provide thermodynamic evidence for SN order, half a century after the theoretical proposal [Blume M, Hsieh YY (1969) J Appl Phys 40:1249; Andreev AF, Grishchuk IA (1984) J Exp Theor Phys 97:467-475].

Expanding frontiers in materials chemistry and physics with multiple anions.

During the last century, inorganic oxide compounds laid foundations for materials synthesis, characterization, and technology translation by adding new functions into devices previously dominated by main-group element semiconductor compounds. Today, compounds with multiple anions beyond the single-oxide ion, such as oxyhalides and oxyhydrides, offer a new materials platform from which superior functionality may arise. Here we review the recent progress, status, and future prospects and challenges facing the development and deployment of mixed-anion compounds, focusing mainly on oxide-derived materials. We devote attention to the crucial roles that multiple anions play during synthesis, characterization, and in the physical properties of these materials. We discuss the opportunities enabled by recent advances in synthetic approaches for design of both local and overall structure, state-of-the-art characterization techniques to distinguish unique structural and chemical states, and chemical/physical properties emerging from the synergy of multiple anions for catalysis, energy conversion, and electronic materials.

Synthesis of anti-perovskite-type carbides and nitrides from metal oxides and melamine.

Four anti-perovskite-type compounds, ZnNNi3, ZnCNi3, SnNCo3, and SnCCo3, are synthesised through reactions between metal oxides and organic compound melamine (C3H6N6). ZnNNi3 and ZnCNi3 are selectively synthesised by choosing different reaction temperatures and nominal oxide-to-melamine ratios. SnNCo3 is synthesised for the first time by this melamine method. Resistivity, magnetisation, and heat capacity measurements reveal that SnNCo3 is a correlated metal with a high density of states at the Fermi level. The results demonstrate that this feasible synthetic route using melamine is useful in the search for complex metal carbides and nitrides toward novel functional materials.