Pressure driven magnetic order in Sr[Formula: see text]Ca[Formula: see text]Co[Formula: see text]P[Formula: see text].

The magnetic phase diagram of Sr[Formula: see text]Ca[Formula: see text]Co[Formula: see text]P[Formula: see text] as a function of hydrostatic pressure and temperature is investigated by means of high pressure muon spin rotation, relaxation and resonance ([Formula: see text]SR). The weak pressure dependence for the [Formula: see text] compounds suggests that the rich phase diagram of Sr[Formula: see text]Ca[Formula: see text]Co[Formula: see text]P[Formula: see text] as a function of x at ambient pressure may not solely be attributed to chemical pressure effects. The [Formula: see text] compound on the other hand reveals a high pressure dependence, where the long range magnetic order is fully suppressed at [Formula: see text] kbar, which seem to be a first order transition. In addition, an intermediate phase consisting of magnetic domains is formed above [Formula: see text] kbar where they co-exist with a magnetically disordered state. These domains are likely to be ferromagnetic islands (FMI) and consist of an high- (FMI-[Formula: see text]) and low-temperature (FMI-[Formula: see text]) region, respectively, separated by a phase boundary at [Formula: see text] K. This kind of co-existence is unusual and is originating from a coupling between lattice and magnetic degrees of freedoms.

Resonant inelastic soft x-ray scattering on LaPt2Si2.

X-ray absorption and resonant inelastic x-ray scattering spectra of LaPt2Si2single crystal at the Si 2pand La 4dedges are presented. The data are interpreted in terms of density functional theory, showing that the Si spectra can be described in terms of Sisanddlocal partial density of states (LPDOS), and the La spectra are due to quasi-atomic local 4fexcitations. Calculations show that Ptd-LPDOS dominates the occupied states, and a sharp localized Lafstate is found in the unoccupied states, in line with the observations.

Indoor radon exposure and its correlation with the radiometric map of uranium in Sweden.

Indoor radon concentrations are controlled by both human factors and geological factors. It is important to separate the anthropogenic and geogenic contributions. We show that there is a positive correlation between the radiometric map of uranium in the ground and the measured radon in the household in Sweden. A map of gamma radiation is used to obtain an equivalent uranium concentration (ppm eU) for each postcode area. The aggregated uranium content is compared to the yearly average indoor radon concentration for different types of houses. Interestingly, modern households show reduced radon concentrations even in postcode areas with high average uranium concentrations. This shows that modern construction is effective at reducing the correlation with background uranium concentrations and minimizing the health risk associated with radon exposure. These correlations and predictive housing parameters could assist in monitoring higher risk areas.

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.

Honeycomb layered oxides: structure, energy storage, transport, topology and relevant insights.

The advent of nanotechnology has hurtled the discovery and development of nanostructured materials with stellar chemical and physical functionalities in a bid to address issues in energy, environment, telecommunications and healthcare. In this quest, a class of two-dimensional layered materials consisting of alkali or coinage metal atoms sandwiched between slabs exclusively made of transition metal and chalcogen (or pnictogen) atoms arranged in a honeycomb fashion have emerged as materials exhibiting fascinatingly rich crystal chemistry, high-voltage electrochemistry, fast cation diffusion besides playing host to varied exotic electromagnetic and topological phenomena. Currently, with a niche application in energy storage as high-voltage materials, this class of honeycomb layered oxides serves as ideal pedagogical exemplars of the innumerable capabilities of nanomaterials drawing immense interest in multiple fields ranging from materials science, solid-state chemistry, electrochemistry and condensed matter physics. In this review, we delineate the relevant chemistry and physics of honeycomb layered oxides, and discuss their functionalities for tunable electrochemistry, superfast ionic conduction, electromagnetism and topology. Moreover, we elucidate the unexplored albeit vastly promising crystal chemistry space whilst outlining effective ways to identify regions within this compositional space, particularly where interesting electromagnetic and topological properties could be lurking within the aforementioned alkali and coinage-metal honeycomb layered oxide structures. We conclude by pointing towards possible future research directions, particularly the prospective realisation of Kitaev-Heisenberg-Dzyaloshinskii-Moriya interactions with single crystals and Floquet theory in closely-related honeycomb layered oxide materials.

Polytypism and superconductivity in the NbS2 system.

We report on the phase formation and the superconducting properties in the NbS2 system. Specifically, we have performed a series of standardized solid-state syntheses in this system, which allow us to establish a comprehensive synthesis map for the formation of the two polytypes 2H-NbS2 and 3R-NbS2, respectively. We show that the identification of two polytypes by means of X-ray diffraction is not always unambiguous. Our physical property measurements on a phase-pure sample of 3R-NbS2, on a phase-pure sample of 2H-NbS2, and a mixed phase sample confirm earlier reports that 2H-NbS2 is a bulk superconductor and that 3R-NbS2 is not a superconductor above T = 1.75 K. Our results clearly show that specific heat measurements, as true bulk measurements, are crucial for the identification of superconducting materials in this and related systems. Our results indicate that for the investigation of van der Waals materials great care has to be taken on choosing the synthesis conditions for obtaining phase pure samples.

Structural Transition with a Sharp Change in the Electrical Resistivity and Spin-Orbit Mott Insulating State in a Rhenium Oxide, Sr3Re2O9.

We report the successful synthesis, crystal structure, and electrical properties of Sr3Re2O9, which contains Re6+ with the 5d1 configuration. This compound is isostructural with Ba3Re2O9 and shows a first-order structural phase transition at ∼370 K. The low-temperature (LT) phase crystallizes in a hettotype structure of Ba3Re2O9, which is different from that of the LT phase of Sr3W2O9, suggesting that the electronic state of Re6+ plays an important role in determining the crystal structure of the LT phase. The structural transition is accompanied by a sharp change in the electrical resistivity. This is likely a metal-insulator transition, as suggested by the electronic band calculation and magnetic susceptibility. In the LT phase, the ReO6 octahedra are rotated in a pseudo-a0a0a+ manner in Glazer notation, which corresponds to C-type orbital ordering. Paramagnetic dipole moments were confirmed to exist in the LT phase by muon spin rotation and relaxation measurements. However, the dipole moments shrink greatly because of the strong spin-orbit coupling in the Re ions. Thus, the electronic state of the LT phase corresponds to a Mott insulating state with strong spin-orbit interactions at the Re sites.

Cation Distributions and Magnetic Properties of Ferrispinel MgFeMnO4.

The crystal structure and magnetic properties of the cubic spinel MgFeMnO4 were studied by using a series of in-house techniques along with large-scale neutron diffraction and muon spin rotation spectroscopy in the temperature range between 1.5 and 500 K. The detailed crystal structure is successfully refined by using a cubic spinel structure described by the space group Fd3̅m. Cations within tetrahedral A and octahedral B sites of the spinel were found to be in a disordered state. The extracted fractional site occupancies confirm the presence of antisite defects, which are of importance for the electrochemical performance of MgFeMnO4 and related battery materials. Neutron diffraction and muon spin spectroscopy reveal a ferrimagnetic order below TC = 394.2 K, having a collinear spin arrangement with antiparallel spins at the A and B sites, respectively. Our findings provide new and improved understanding of the fundamental properties of the ferrispinel materials and of their potential applications within future spintronics and battery devices.

Magnetism and ion diffusion in honeycomb layered oxide [Formula: see text].

In the quest for developing novel and efficient batteries, a great interest has been raised for sustainable K-based honeycomb layer oxide materials, both for their application in energy devices as well as for their fundamental material properties. A key issue in the realization of efficient batteries based on such compounds, is to understand the K-ion diffusion mechanism. However, investigation of potassium-ion (K[Formula: see text]) dynamics in materials using e.g. NMR and related techniques has so far been very challenging, due to its inherently weak nuclear magnetic moment, in contrast to other alkali ions such as lithium and sodium. Spin-polarised muons, having a high gyromagnetic ratio, make the muon spin rotation and relaxation ([Formula: see text]SR) technique ideal for probing ions dynamics in these types of energy materials. Here we present a study of the low-temperature magnetic properties as well as K[Formula: see text] dynamics in honeycomb layered oxide material [Formula: see text] using mainly the [Formula: see text]SR technique. Our low-temperature [Formula: see text]SR results together with complementary magnetic susceptibility measurements find an antiferromagnetic transition at [Formula: see text] K. Further [Formula: see text]SR studies performed at higher temperatures reveal that potassium ions (K[Formula: see text]) become mobile above 200 K and the activation energy for the diffusion process is obtained as [Formula: see text] meV. This is the first time that K[Formula: see text] dynamics in potassium-based battery materials has been measured using [Formula: see text]SR. Assisted by high-resolution neutron diffraction, the temperature dependence of the K-ion self diffusion constant is also extracted. Finally our results also reveal that K-ion diffusion occurs predominantly at the surface of the powder particles. This opens future possibilities for potentially improving ion diffusion as well as K-ion battery device performance using nano-structuring and surface coatings of the particles.

High-voltage honeycomb layered oxide positive electrodes for rechargeable sodium batteries.

Honeycomb layered oxides from Na2Ni2-xCoxTeO6 family were assessed for use as positive electrodes in rechargeable sodium batteries at ambient and elevated temperatures using ionic liquids. Substitution of nickel with cobalt increases the discharge voltage to nearly 4 V (versus Na+/Na), surpassing the average voltages of most Na based layered oxide positive electrodes.

Quantifying Diffusion through Interfaces of Lithium-Ion Battery Active Materials.

Detailed understanding of charge diffusion processes in a lithium-ion battery is crucial to enable its systematic improvement. Experimental investigation of diffusion at the interface between active particles and the electrolyte is challenging but warrants investigation as it can introduce resistances that, for example, limit the charge and discharge rates. Here, we show an approach to study diffusion at interfaces using muon spin spectroscopy. By performing measurements on LiFePO4 platelets with different sizes, we determine how diffusion through the LiFePO4 (010) interface differs from that in the center of the particle (i.e., bulk diffusion). We perform ab initio calculations to aid the understanding of the results and show the relevance of our interfacial diffusion measurement to electrochemical performance through cyclic voltammetry measurements. These results indicate that surface engineering can be used to improve the performance of lithium-ion batteries.

Tomonaga-Luttinger Liquid Spin Dynamics in the Quasi-One-Dimensional Ising-Like Antiferromagnet BaCo_{2}V_{2}O_{8}.

Combining inelastic neutron scattering and numerical simulations, we study the quasi-one-dimensional Ising anisotropic quantum antiferromagnet BaCo_{2}V_{2}O_{8} in a longitudinal magnetic field. This material shows a quantum phase transition from a Néel ordered phase at zero field to a longitudinal incommensurate spin density wave at a critical magnetic field of 3.8 T. Concomitantly, the excitation gap almost closes and a fundamental reconfiguration of the spin dynamics occurs. These experimental results are well described by the universal Tomonaga-Luttinger liquid theory developed for interacting spinless fermions in one dimension. We especially observe the rise of mainly longitudinal excitations, a hallmark of the unconventional low-field regime in Ising-like quantum antiferromagnetic chains.

Linear Trimer Formation with Antiferromagnetic Ordering in 1T-CrSe2 Originating from Peierls-like Instabilities and Interlayer Se-Se Interactions.

Anomalous successive structural transitions in layered 1T-CrSe2 with an unusual Cr4+ valency were investigated by synchrotron X-ray diffraction. 1T-CrSe2 exhibits dramatic structural changes in in-plane Cr-Cr and interlayer Se-Se distances, which originate from two interactions: (i) in-plane Cr-Cr interactions derived from Peierls-like trimerization instabilities on the orbitally assisted one-dimensional chains and (ii) interlayer Se-Se interactions through p-p hybridization. As a result, 1T-CrSe2 has the unexpected ground state of an antiferromagnetic metal with multiple Cr linear trimers with three-center-two-electron σ bonds. Interestingly, partial substitution of Se for S atoms in 1T-CrSe2 changes the ground state from an antiferromagnetic metal to an insulator without long-range magnetic ordering, which is due to the weakening of interlayer interactions between anions. The unique low-temperature structures and electronic states of this system are determined by the competition and cooperation of in-plane Cr-Cr and interlayer Se-Se interactions.

Magnetic phase diagram of K2Cr8O16 clarified by high-pressure muon spin spectroscopy.

The K2Cr8O16 compound belongs to a series of quasi-1D compounds with intriguing magnetic properties that are stabilized through a high-pressure synthesis technique. In this study, a muon spin rotation, relaxation and resonance (µ+SR) technique is used to investigate the pressure dependent magnetic properties up to 25 kbar. µ+SR allows for measurements in true zero applied field and hereby access the true intrinsic material properties. As a result, a refined temperature/pressure phase diagram is presented revealing a novel low temperature/high pressure (pC1 = 21 kbar) transition from a ferromagnetic insulating to a high-pressure antiferromagnetic insulator. Finally, the current study also indicates the possible presence of a quantum critical point at pC2 ~ 33 kbar where the magnetic order in K2Cr8O16 is expected to be fully suppressed even at T = 0 K.

Li-ion diffusion in Li intercalated graphite C6Li and C12Li probed by µ+SR.

In order to study a diffusive behavior of Li+ in Li intercalated graphites, we have measured muon spin relaxation (µ+SR) spectra for C6Li and C12Li synthesized with an electrochemical reaction between Li and graphite in a Li-ion battery. For both compounds, it was found that Li+ ions start to diffuse above 230 K and the diffusive behavior obeys a thermal activation process. The activation energy (Ea) for C6Li is obtained as 270(5) meV, while Ea = 170(20) meV for C12Li. Assuming a jump diffusion of Li+ in the Li layer of C6Li and C12Li, a self-diffusion coefficient DLi at 310 K was estimated as 7.6(3) × 10-11 (cm2 s-1) in C6Li and 14.6(4) × 10-11 (cm2 s-1) in C12Li.

Prismatic analyser concept for neutron spectrometers.

Developments in modern neutron spectroscopy have led to typical sample sizes decreasing from few cm to several mm in diameter samples. We demonstrate how small samples together with the right choice of analyser and detector components makes distance collimation an important concept in crystal analyser spectrometers. We further show that this opens new possibilities where neutrons with different energies are reflected by the same analyser but counted in different detectors, thus improving both energy resolution and total count rate compared to conventional spectrometers. The technique can readily be combined with advanced focussing geometries and with multiplexing instrument designs. We present a combination of simulations and data showing three different energies simultaneously reflected from one analyser. Experiments were performed on a cold triple axis instrument and on a prototype inverse geometry Time-of-flight spectrometer installed at PSI, Switzerland, and shows excellent agreement with the predictions. Typical improvements will be 2.0 times finer resolution and a factor of 1.9 in flux gain compared to a focussing Rowland geometry, or of 3.3 times finer resolution and a factor of 2.4 in flux gain compared to a single flat analyser slab.

Magnetic structure of the metallic triangular antiferromagnet Ag2NiO2.

The magnetic structure of the metallic antiferromagnet Ag2NiO2 with the Néel temperature TN = 56 K has been investigated by means of a neutron diffraction technique using a powder sample in the temperature range between 5 and 65 K. The antiferromagnetic (AF) diffraction peaks are clearly observed below TN and can be indexed with the propagation vector [Formula: see text]. Based on the results of both a representational analysis and a Rietveld refinement of the magnetic peaks, the AF spin structure is determined as an A-type AF structure with ml = m0cos(2πk ⋅l), where ml is the moment at the lth Ni(3+) site and m0 = (0.31,0,0.65) µB at 5 K.

Li diffusion in LixCoO2 probed by muon-spin spectroscopy.

The diffusion coefficient of Li+ ions (D(Li)) in the battery material LixCoO2 has been investigated by muon-spin relaxation (mu+SR). Based on experiments in zero and weak longitudinal fields at temperatures up to 400 K, we determined the fluctuation rate (nu) of the fields on the muons due to their interaction with the nuclear moments. Combined with susceptibility data and electrostatic potential calculations, clear Li+ ion diffusion was detected above approximately 150 K. The D(Li) estimated from nu was in very good agreement with predictions from first-principles calculations, and we present the mu+SR technique as an optimal probe to detect D(Li) for materials containing magnetic ions.

Application of capillary electrophoresis mass spectrometry and liquid chromatography multiple-step tandem electrospray mass spectrometry to profile glycoform expression during Haemophilus influenzae pathogenesis in the chinchilla model of experimental otitis media.

Otitis media caused by nontypeable Haemophilus influenzae (NTHi) is a common and recurrent bacterial infection of childhood. The structural variability and diversity of H. influenzae lipopolysaccharide (LPS) glycoforms are known to play a significant role in the commensal and disease-causing behavior of this pathogen. In this study, we determined LPS glycoform populations from NTHi strain 1003 during the course of experimental otitis media in the chinchilla model of infection by mass spectrometric techniques. Building on an established structural model of the major LPS glycoforms expressed by this NTHi strain in vitro (M. Månsson, W. Hood, J. Li, J. C. Richards, E. R. Moxon, and E. K. Schweda, Eur. J. Biochem. 269:808-818, 2002), minor isomeric glycoform populations were determined by liquid chromatography multiple-step tandem electrospray mass spectrometry (LC-ESI-MS(n)). Using capillary electrophoresis ESI-MS (CE-ESI-MS), we determined glycoform profiles for bacteria from direct middle ear fluid (MEF) samples. The LPS glycan profiles were essentially the same when the MEF samples of 7 of 10 animals were passaged on solid medium (chocolate agar). LC-ESI-MS(n) provided a sensitive method for determining the isomeric distribution of LPS glycoforms in MEF and passaged specimens. To investigate changes in LPS glycoform distribution during the course of infection, MEF samples were analyzed at 2, 5, and 9 days postinfection by CE-ESI-MS following minimal passage on chocolate agar. As previously observed, sialic acid-containing glycoforms were detected during the early stages of infection, but a trend toward more-truncated and less-complex LPS glycoforms that lacked sialic acid was found as disease progressed.

On-board sample cleaver.

An on-board sample cleaver has been developed in order to cleave small and hard-to-cleave samples. To acquire good cleaves from rigid samples the alignment of the cleaving blade with respect to the internal crystallographic planes is crucial. To have the opportunity to mount the sample and align it to the blade ex situ has many advantages. The design presented has allowed us to cleave very tiny and rigid samples, e.g., the high-temperature superconductor La((2-x))Sr(x)CuO(4). Further, in this design the sample and the cleaver will have the same temperature, allowing us to cleave and keep the sample at low temperature. This is a big advantage over prior cleaver systems. As a result, better surfaces and alignments can be realized, which considerably simplifies and improves the experiments.