Local electronic structure of interstitial hydrogen in MgH2inferred from muon study.

Magnesium hydride has great potential as a solid hydrogen (H) storage material because of its high H storage capacity of 7.6 wt%. However, its slow hydrogenation and dehydrogenation kinetics and the high temperature of 300 ∘C required for decomposition are major obstacles to small-scale applications such as automobiles. The local electronic structure of interstitial H in MgH2is an important fundamental knowledge in solving this problem, which has been studied mainly based on density functional theory (DFT). However, few experimental studies have been performed to assess the results of DFT calculations. We have therefore introduced muon (Mu) as pseudo-H into MgH2and investigated the corresponding interstitial H states by analyzing their electronic and dynamical properties in detail. As a result, we observed multiple Mu states similar to those observed in wide-gap oxides, and found that their electronic states can be attributed to relaxed-excited states associated with donor/acceptor levels predicted by the recently proposed 'ambipolarity model'. This provides an indirect support for the DFT calculations on which the model is based via the donor/acceptor levels. An important implication of the muon results for improved hydrogen kinetics is that dehydrogenation, serving as areductionfor hydrides, stabilises the interstitial H-state.

Organic molecular dynamics and charge-carrier lifetime in lead iodide perovskite MAPbI3.

The long charge carrier lifetime of the hybrid organic-inorganic perovskites (HOIPs) is the key for their remarkable performance as a solar cell material. The microscopic mechanism for the long lifetime is still in debate. Here, by using a muon spin relaxation technique that probes the fluctuation of local magnetic fields, we show that the muon depolarization rate (Δ) of a prototype HOIP methylammonium lead iodide (MAPbI3) shows a sharp decrease with increasing temperature in two steps above 120 K and 190 K across the structural transition from orthorhombic to tetragonal structure at 162 K. Our analysis shows that the reduction of Δ is quantitatively in agreement with the expected behavior due to the rapid development of methyl ammonium (MA) jumping rotation around the C 3 and C 4 symmetry axes. Our results provide direct evidence for the intimate relation between the rotation of the electric dipoles of MA molecules and the charge carrier lifetime in HOIPs.

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.

Na Diffusion in Hard Carbon Studied with Positive Muon Spin Rotation and Relaxation.

The diffusive nature of Na+ in Na-inserted hard carbon (C x Na), which is the most common anode material for a Na-ion battery, was studied with a positive muon spin rotation and relaxation (µ+SR) technique in transverse, zero, and longitudinal magnetic fields (TF, ZF, and LF) at temperatures between 50 and 375 K, where TF (LF) denotes the applied magnetic field perpendicular (parallel) to the initial muon spin polarization. At temperatures above 150 K, TF-µ+SR measurements showed a distinct motional narrowing behavior, implying that Na+ begins to diffuse above 150 K. The presence of two different muon sites in C x Na was confirmed with ZF- and LF-µ+SR measurements; one is in the Na-inserted graphene layer, and the other is in the Na-vacant graphene layer adjacent to the Na-inserted graphene layer. A systematic increase in the field fluctuation rate (ν) with increasing temperature also evidenced a thermally activated Na diffusion, particularly above 150 K. Assuming the two-dimensional diffusion of Na+ in the graphene layers, the self-diffusion coefficient of Na+ (D Na J) at 300 K was estimated to be 2.5 × 10-11 cm2/s with a thermal activation energy of 39(7) meV.

Observation of Cu Spin Fluctuations in High-Tc Cuprate Superconductor Nanoparticles Investigated by Muon Spin Relaxation.

The nano-size effects of high-Tc cuprate superconductor La2-xSrxCuO4 with x = 0.20 are investigated using X-ray diffractometry, Transmission electron microscopy, and muon-spin relaxation (µSR). It is investigated whether an increase in the bond distance of Cu and O atoms in the conducting layer compared to those of the bulk state might affect its physical and magnetic properties. The µSR measurements revealed the slowing down of Cu spin fluctuations in La2-xSrxCuO4 nanoparticles, indicating the development of a magnetic correlation at low temperatures. The magnetic correlation strengthens as the particle size reduces. This significantly differs from those observed in the bulk form, which show a superconducting state below Tc. It is indicated that reducing the particle size of La2-xSrxCuO4 down to nanometer size causes the appearance of magnetism. The magnetism enhances with decreasing particle size.

Na-ion mobility in P2-type Na0.5MgxNi0.17-xMn0.83O2 (0 ≤ x ≤ 0.07) from electrochemical and muon spin relaxation studies.

Sodium transition metal oxides with a layered structure are one of the most widely studied cathode materials for Na+-ion batteries. Since the mobility of Na+ in such cathode materials is a key factor that governs the performance of material, electrochemical and muon spin rotation and relaxation techniques are here used to reveal the Na+-ion mobility in a P2-type Na0.5MgxNi0.17-xMn0.83O2 (x = 0, 0.02, 0.05 and 0.07) cathode material. Combining electrochemical techniques such as galvanostatic cycling, cyclic voltammetry, and the galvanostatic intermittent titration technique with µ+SR, we have successfully extracted both self-diffusion and chemical-diffusion under a potential gradient, which are essential to understand the electrode material from an atomic-scale viewpoint. The results indicate that a small amount of Mg substitution has strong effects on the cycling performance and the Na+ mobility. Amongst the tested cathode systems, it was found that the composition with a Mg content of x = 0.02 resulted in the best cycling stability and highest Na+ mobility based on electrochemical and µ+SR results. The current study clearly shows that for developing a new generation of sustainable energy-storage devices, it is crucial to study and understand both the structure as well as dynamics of ions in the material on an atomic level.

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.

Extreme Suppression of Antiferromagnetic Order and Critical Scaling in a Two-Dimensional Random Quantum Magnet.

Sr_{2}CuTeO_{6} is a square-lattice Néel antiferromagnet with superexchange between first-neighbor S=1/2 Cu spins mediated by plaquette centered Te ions. Substituting Te by W, the affected impurity plaquettes have predominantly second-neighbor interactions, thus causing local magnetic frustration. Here we report a study of Sr_{2}CuTe_{1-x}W_{x}O_{6} using neutron diffraction and µSR techniques, showing that the Néel order vanishes already at x=0.025±0.005. We explain this extreme order suppression using a two-dimensional Heisenberg spin model, demonstrating that a W-type impurity induces a deformation of the order parameter that decays with distance as 1/r^{2} at temperature T=0. The associated logarithmic singularity leads to loss of order for any x>0. Order for small x>0 and T>0 is induced by weak interplane couplings. In the nonmagnetic phase of Sr_{2}CuTe_{1-x}W_{x}O_{6}, the µSR relaxation rate exhibits quantum critical scaling with a large dynamic exponent, z≈3, consistent with a random-singlet state.

Gapless spin liquid in a square-kagome lattice antiferromagnet.

Observation of a quantum spin liquid (QSL) state is one of the most important goals in condensed-matter physics, as well as the development of new spintronic devices that support next-generation industries. The QSL in two dimensional quantum spin systems is expected to be due to geometrical magnetic frustration, and thus a kagome-based lattice is the most probable playground for QSL. Here, we report the first experimental results of the QSL state on a square-kagome quantum antiferromagnet, KCu6AlBiO4(SO4)5Cl. Comprehensive experimental studies via magnetic susceptibility, magnetisation, heat capacity, muon spin relaxation (µSR), and inelastic neutron scattering (INS) measurements reveal the formation of a gapless QSL at very low temperatures close to the ground state. The QSL behavior cannot be explained fully by a frustrated Heisenberg model with nearest-neighbor exchange interactions, providing a theoretical challenge to unveil the nature of the QSL state.

Quantum magnetisms in uniform triangular lattices Li2AMo3O8 (A = In, Sc).

Molecular based spin-1/2 triangular lattice systems such as LiZn2Mo3O8 have attracted research interest. Distortions, defects, and intersite disorder are suppressed in such molecular-based magnets, and intrinsic geometrical frustration gives rise to unconventional and unexpected ground states. Li2AMo3O8 (A = In or Sc) is such a compound where spin-1/2 Mo3O13 clusters in place of Mo ions form the uniform triangular lattice. Their ground states are different according to the A site. Li2InMo3O8 undergoes conventional 120° long-range magnetic order below TN = 12 K whereas isomorphic Li2ScMo3O8 exhibits no long-range magnetic order down to 0.5 K. Here, we report exotic magnetisms in Li2InMo3O8 and Li2ScMo3O8 investigated by muon spin rotation (µSR) and inelastic neutron scattering (INS) spectroscopies using polycrystalline samples. Li2InMo3O8 and Li2ScMo3O8 show completely different behaviors observed in both µSR and INS measurements, representing their different ground states. Li2InMo3O8 exhibits spin wave excitation which is quantitatively described by the nearest neighbor anisotropic Heisenberg model based on the 120° spin structure. In contrast, Li2ScMo3O8 undergoes short-range magnetic order below 4 K with quantum-spin-liquid-like magnetic fluctuations down to the base temperature. Origin of the different ground states is discussed in terms of anisotropies of crystal structures and magnetic interactions.

Nuclear Magnetic Field in Solids Detected with Negative-Muon Spin Rotation and Relaxation.

Using an intense negative muon (µ^{-}) source, we have studied the internal magnetic fields in a powder sample of magnesium hydride (MgH_{2}). By extracting the signal from the µ^{-} captured on Mg nuclei, we found that the negative muon spin rotation and relaxation (µ^{-}SR) spectra clearly showed a Kubo-Toyabe-type relaxation, which indicates a random magnetic field at the Mg site. The field distribution width obtained is very consistent with the predicted value at the Mg site estimated by dipole field calculations, supporting our claim to have observed the nuclear magnetic fields of hydrogens in MgH_{2}. As is the case with µ^{+}SR, µ^{-}SR promises to soon be an indispensable tool for materials analyses.

Development of Ferromagnetic Fluctuations in Heavily Overdoped (Bi,Pb)_{2}Sr_{2}CuO_{6+δ} Copper Oxides.

We demonstrate the presence of ferromagnetic (FM) fluctuations in the superconducting and nonsuperconducting heavily overdoped regimes of high-temperature superconducting copper oxides, using (Bi,Pb)_{2}Sr_{2}CuO_{6+δ} (Bi-2201) single crystals. Magnetization curves exhibit a tendency to be saturated in high magnetic fields at low temperatures in the heavily overdoped crystals, which is probably a precursor phenomenon of a FM transition at a lower temperature. Muon spin relaxation detects the enhancement of spin fluctuations at high temperatures below 200 K. Correspondingly, the ab-plane resistivity follows a 4/3 power law in a wide temperature range, which is characteristic of metals with two-dimensional FM fluctuations due to itinerant electrons. As the Wilson ratio evidences the enhancement of spin fluctuations with hole doping in the heavily overdoped regime, it is concluded that two-dimensional FM fluctuations reside in the heavily overdoped Bi-2201 cuprates, which is probably related to the decrease in the superconducting transition temperature in the heavily overdoped cuprates.

Possible Tomonaga-Luttinger spin liquid state in the spin-1/2 inequilateral diamond-chain compound K3Cu3AlO2(SO4)4.

K3Cu3AlO2(SO4)4 is a highly one-dimensional spin-1/2 inequilateral diamond-chain antiferromagnet. Spinon continuum and spin-singlet dimer excitations are observed in the inelastic neutron scattering spectra, which is in excellent agreement with a theoretical prediction: a dimer-monomer composite structure, where the dimer is caused by strong antiferromagnetic (AFM) coupling and the monomer forms an almost isolated quantum AFM chain controlling low-energy excitations. Moreover, muon spin rotation/relaxation spectroscopy shows no long-range ordering down to 90 mK, which is roughly three orders of magnitude lower than the exchange interaction of the quantum AFM chain. K3Cu3AlO2(SO4)4 is, thus, regarded as a compound that exhibits a Tomonaga-Luttinger spin liquid behavior at low temperatures close to the ground state.

Large Magnetovolume Effect Induced by Embedding Ferromagnetic Clusters into Antiferromagnetic Matrix of Cobaltite Perovskite.

Materials that show negative thermal expansion (NTE) have significant industrial merit because they can be used to fabricate composites whose dimensions remain invariant upon heating. In some materials, NTE is concomitant with the spontaneous magnetization due to the magnetovolume effect (MVE). Here the authors report a new class of MVE material; namely, a layered perovskite PrBaCo2 O5.5+x (0 ≤ x ≤ 0.41), in which strong NTE [ß ≈ -3.6 × 10-5 K-1 (90-110 K) at x = 0.24] is triggered by embedding ferromagnetic (F) clusters into the antiferromagnetic (AF) matrix. The strongest MVE is found near the boundary between F and AF phases in the phase diagram, indicating the essential role of competition between the F-clusters and the AF-matrix. Furthermore, the MVE is not limited to the PrBaCo2 O5.5+x but is also observed in the NdBaCo2 O5.5+x . The present study provides a new approach to obtaining MVE and offers a path to the design of NTE materials.

Muonium in stishovite: implications for the possible existence of neutral atomic hydrogen in the earth's deep mantle.

Hydrogen in the Earth's deep interior has been thought to exist as a hydroxyl group in high-pressure minerals. We present Muon Spin Rotation experiments on SiO2 stishovite, which is an archetypal high-pressure mineral. Positive muon (which can be considered as a light isotope of proton) implanted in stishovite was found to capture electron to form muonium (corresponding to neutral hydrogen). The hyperfine-coupling parameter and the relaxation rate of spin polarization of muonium in stishovite were measured to be very large, suggesting that muonium is squeezed in small and anisotropic interstitial voids without binding to silicon or oxygen. These results imply that hydrogen may also exist in the form of neutral atomic hydrogen in the deep mantle.

Magnetic ground-state of perovskite PbVO3 with large tetragonal distortion.

The magnetic properties of PbVO 3, a PbTiO 3-type perovskite with a large tetragonal distortion ( c/a = 1.229), were investigated. The temperature dependence of the measured magnetization of multidomain single-crystal samples showed a broad maximum centered around 180 K, indicating a two-dimensional antiferromagnetism. muSR measurement revealed the presence of a long-range order below 43 K. The two-dimensional magnetism is due to the ordering of d xy orbitals, which is thought to also be related to the large tetragonal distortion of PbVO 3.