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Ketene, a versatile reagent in production of fine and specialty chemicals, is produced from acetic acid. We investigate the synthesis of ketene from acetic acid over the (3,0;1,1) surface of Cu2O(1 0 0) through analysis of the adsorption and desorption characteristics of formic and acetic acids. The results allow us to establish a reaction mechanism for ketene formation. Observations from x-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy, and temperature programmed desorption (TPD), supported by a comparison with formic acid results, suggest that acetic acid reacts with Cu2O through deprotonation to form acetate species coordinated to copper sites and hydroxylation of nearby surface oxygen sites. For formic acid the decomposition of adsorbed formate species results in desorption of CO2 and CO while, for acetic acid, high yields of ketene are observed at temperature >500 K. Modeling by density functional theory (DFT) confirms the strong interaction of acetic acid with the (3,0;1,1) surface and the spontaneous dissociation into adsorbed acetate and hydrogen atom species, the latter forming an OH-group. In an identified reaction intermediate ketene binds via all C and O atoms to Cu surface sites, in agreement with interpretations from XPS. In the vicinity of the adsorbate the surface experiences a local reorganization into a c(2 × 2) reconstruction. The total computed energy barrier for ketene formation is 1.81 eV in good agreement with the 1.74 eV obtained from TPD analysis. Our experimental observations and mechanistic DFT studies suggests that Cu2O can operate as an efficient catalyst for the green generation of ketene from acetic acid., Swedish Research Council (VR); VR Starting Grant; Knut och Alice Wallenbergs stiftelse; STINT Joint China-Sweden Mobility Program; Ragnar Holm Foundation; Trygger’s Foundation; Chalmers Areas of Advance-Materials Science

For quantum systems or materials, a common procedure for probing their behaviour is to tune electronic/magnetic properties using external parameters, e.g. temperature, magnetic field or pressure. Pressure application as an external stimuli is a widely used tool, where the sample in question is inserted into a pressure cell providing a hydrostatic pressure condition. Such device causes some practical problems when using in Muon Spin Rotation/Relaxation ($\mu^+$SR) experiments as a large proportion of the muons will be implanted in the pressure cell rather than in the sample, resulting in a higher background signal. This issue gets further amplified when the temperature dependent response from the sample is much smaller than that of the pressure cell,which may cause the sample response to be lost in the background and cause difficulties in aligning the sample within the beam. To tackle this issue, we have used pySRIM to construct a practical and helpful simulation tool for calculating muon stopping fractions, specifically for the pressure cell setup at the $\mu$E1 beamline using the GPD spectrometer at the Paul Scherrer Institute, with the use of TRIM simulations. The program is used to estimate the number of muon stopping in both the sample and the pressure cell at a given momentum. The simulation tool is programmed into a GUI, making it accessible to user to approximate prior to their experiments at GPD what fractions will belong to the sample and the pressure cell in their fitting procedure., Comment: 8 Pages, 3 Figures, Conference proceedings for 15th international conference on muon spin rotation, relaxation and resonance

Rhenium oxides belonging to the family AReO4 where A is a metal cation, exhibit interesting electronic and magnetic properties. In this study we have utilized the muon spin rotation/relaxation (µ +SR) technique to study the magnetic properties of the MgReO4 compound. To the best of our knowledge, this is the first investigation reported on this interesting material, that is stabilized in a wolframite crystal structure using a special high-pressure synthesis technique. Bulk magnetic studies show the onset of an antiferromagnetic (AF) long range order, or a possible singlet spin state at T C1 ≈ 90 K, with a subtle second high-temperature transition at T C2 ≈ 280 K. Both transitions are also confirmed by heat capacity (Cp ) measurements. From our µ +SR measurements, it is clear that the sample enters an AF order below T C1 = T N ≈ 85 K. We find no evidence of magnetic signal above T N, which indicates that T C2 is likely linked to a structural transition. Further, via sensitive zero field (ZF) µ +SR measurements we find evidence of a spin reorientation at T Cant ≈ 65 K. This points towards a transition from a collinear AF into a canted AF order at low temperature, which is proposed to be driven by competing magnetic interactions.

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.

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.

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 mu+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 mu+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. Title in dissertation list of papers: Na-mobility in P2-type Na0.5MgxNi0.17−xMn0.83O2 (0 ≤ x ≤ 0.07) from electrochemical and muon-spin relaxation studies

The internal nuclear magnetic field in a superconducting MgB2 powder sample was studied with a µ− SR technique. Although the past µ +SR study on MgB2 reported the appearance of a dynamic behavior even below Tc due to µ + diffusion, µ− SR shows a static behavior in the whole temperature range measured, as expected. The ZF-µ− SR spectra do not suggest any appearance of additional magnetic field below Tc within the experimental accuracy. Considering the small asymmetry of the µ− SR signal, it is a challenge to detect the appearance of an internal magnetic field below Tc caused by the time reversal symmetry breaking.

In an all solid state Li-ion battery, it is crucial to reduce ionic resistivity at the interface between the electrode and the electrolyte in order to enhance Li+ mobility across the interface. Recent first principles calculations predict the presence of a space-charge layer (SCL) at the interface due to the difference in the Li+ chemical potential at the interface between two different materials, as in the metal-semiconductor junction in electronic devices. However, the presence of SCL has never been experimentally observed. Our first attempt in a fresh multilayer sample, Cu(10 nm)/Li3PO4(50 nm)/LiCoO2(100 nm) on a sapphire substrate, with low-energy µ +SR (LE µ +SR) revealed a gradual change in the nuclear magnetic field distribution width as a function of implantation depth even across the interface between Li3PO4 and LiCoO2. This implies that the change in the field distribution width at SCL of the sample is too small to be detected by LE µ +SR.

X-ray absorption and resonant inelastic x-ray scattering spectra of LaPt

LiFePO$_4$ (LFPO) is an archetypical and well-known cathode material for rechargeable Li-ion batteries. However, its quasi-one-dimensional (Q1D) structure along with the Fe ions, LFPO also displays interesting low-temperature magnetic properties. Our team has previously utilized the muon spin rotation ($\mu^+$SR) technique to investigate both magnetic spin order as well as Li-ion diffusion in LFPO. In this initial study we extend our investigation and make use of high-pressure $\mu^+$SR to investigate effects on the low-$T$ magnetic order. Contrary to theoretical predictions we find that the magnetic ordering temperature as well as the ordered magnetic moment increase at high pressure (compressive strain)., Comment: 8 pages, 6 figures, submitted as a part of the International Conference on Muon Spin Rotation, Relaxation and Resonance 2022. Accepted Dec 2022

The magnetic phase diagram of Sr$_{1-x}$Ca$_x$Co$_2$P$_2$ as a function of hydrostatic pressure and temperature is investigated by means of high pressure muon spin rotation, relaxation and resonance ($\mu^+$SR). The weak pressure dependence for the $x\neq1$ compounds suggests that the rich phase diagram of Sr$_{1-x}$Ca$_x$Co$_2$P$_2$ as a function of $x$ at ambient pressure may not only be attributed to solely chemical pressure effects. The $x=1$ compound on the other hand reveals a high pressure dependence, where the long range magnetic order is fully suppressed at $p_{\rm c2}\approx9.8$~kbar, which seem to be a first order transition. In addition, an intermediate phase consisting of dilute ferromagnetic islands (FMI) is formed above $p_{\rm c1}\approx8$~kbar where they co-exist with a magnetically disordered state. Moreover, such FMI phase seems to consist of an high- (FMI-\textcircled{\small{1}}) and low-temperature (FMI-\textcircled{\small{2}}) region, respectively, separated by a phase boundary at $T_{\rm i}\approx20$~K., Comment: 10 pages, 8 figures

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., MgFeMnO4 crystallizes in the typical cubic spinel with cation disordering between the tetrahedra A and the octahedra B sites. Combining the in-house experiments with neutron (n0) and muon (μ+) techniques, we reveal (i) the accurate crystal structure and site occupancy of MgFeMnO4 at 300 and 500 K, (ii) clear presence of antisite defects that have importance for the compound’s electrochemical performance, and (iii) MgFeMnO4 enters into a collinear ferrimagnetic ordering below TC = 394.2 K.

The magnetic ground states in highly ordered double perovskites LaSr1−xCaxNiReO6 (x = 0.0, 0.5, 1.0) are studied in view of the Goodenough-Kanamori rules of superexchange interactions in this paper. In LaSrNiReO6, Ni and Re sublattices are found to exhibit curious magnetic states separately, but no long range magnetic ordering is achieved. The magnetic transition at ~255 K is identified with the independent Re sublattice magnetic ordering. Interestingly, the sublattice interactions are tuned by modifying the Ni-O-Re bond angles through Ca doping. Upon Ca doping, the Ni and Re sublattices start to display a ferrimagnetically ordered state at low temperature. The neutron powder diffraction data reveals long range ferrimagnetic ordering of the Ni and Re magnetic sublattices along the crystallographic b-axis. The transition temperature of the ferrimagnetic phase increases monotonically with increasing Ca concentration.

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- ...

In this work, we present the CoESCA station for electron-electron coincidence spectroscopy from surfaces, built in a close collaboration between Uppsala University and Helmholtz-Zentrum Berlin at the BESSY II synchrotron facility in Berlin, Germany. We start with a detailed overview of previous work in the field of electron-electron coincidences, before we describe the CoESCA setup and its design parameters. The system is capable of recording shot-to-shot resolved 6D coincidence datasets, i.e. the kinetic energy and the two take off angles for both coincident electrons. The mathematics behind extracting and analysing these multi-dimensional coincidence datasets is introduced, with a focus on coincidence statistics, resulting in fundamental limits of the signal-to-noise ratio and its implications for acquisition times and the size of the raw data stream. The functionality of the CoESCA station is demonstrated for the example of Auger electron - photoelectron coincidences from silver surfaces for photoelectrons from the Ag 3d core levels and their corresponding MNN Auger electrons. The Auger spectra originating from the different core levels, 3d$_{3/2}$ and 3d$_{5/2}$ could be separated and further, the two-hole state energy distributions were determined for these Auger decay channels., 14 pages, 6 figures

Electron-phonon and electron-electron interactions are found to cooperatively drive the long-range charge order in cuprates., Charge order is universal to all hole-doped cuprates. Yet, the driving interactions remain an unsolved problem. Electron-electron interaction is widely believed to be essential, whereas the role of electron-phonon interaction is unclear. We report an ultrahigh-resolution resonant inelastic x-ray scattering (RIXS) study of the in-plane bond-stretching phonon mode in stripe-ordered cuprate La1.675Eu0.2Sr0.125CuO4. Phonon softening and lifetime shortening are found around the charge ordering wave vector. In addition to these self-energy effects, the electron-phonon coupling is probed by its proportionality to the RIXS cross section. We find an enhancement of the electron-phonon coupling around the charge-stripe ordering wave vector upon cooling into the low-temperature tetragonal structure phase. These results suggest that, in addition to electronic correlations, electron-phonon coupling contributes substantially to the emergence of long-range charge-stripe order in cuprates.

The magnetic nature of a quasi-one-dimensional compound, ${\mathrm{BaVSe}}_{3}$, has been investigated with positive muon spin rotation and relaxation (${\ensuremath{\mu}}^{+}\mathrm{SR}$) measurements at ambient and high pressures. At ambient pressure, the ${\ensuremath{\mu}}^{+}\mathrm{SR}$ spectrum recorded under zero external magnetic field exhibited a clear oscillation below the Curie temperature (${T}_{C}\ensuremath{\sim}41\phantom{\rule{0.16em}{0ex}}\mathrm{K}$) due to the formation of quasistatic ferromagnetic order. The oscillation consisted of two different muon spin precession signals, indicating the presence of two magnetically different muon sites in the lattice. However, the two precession frequencies, which correspond to the internal magnetic fields at the two muon sites, could not be adequately explained with relatively simple ferromagnetic structures using the muon sites predicted by density functional theory calculations. The detailed analysis of the internal magnetic field suggested that the V moments align ferromagnetically along the $c$ axis but slightly canted toward the $a$ axis by ${28}^{\ensuremath{\circ}}$ that is coupled antiferromagnetically. The ordered V moment (${\mathbit{M}}_{\mathrm{V}}$) is estimated as (0.59, 0, 1.11) ${\ensuremath{\mu}}_{\mathrm{B}}$. As pressure increased from ambient pressure, ${T}_{C}$ was found to decrease slightly up to about 1.5 GPa, at which point ${T}_{C}$ started to increase rapidly with the further increase of the pressure. Based on a strong ferromagnetic interaction along the $c$ axis, the high-pressure ${\ensuremath{\mu}}^{+}\mathrm{SR}$ result revealed that there are two magnetic interactions in the $ab$ plane; one is an antiferromagnetic interaction that is enhanced with pressure, mainly at pressures below 1.5 GPa, while the other is a ferromagnetic interaction that becomes predominant at pressures above 1.5 GPa.

We report an angle-resolved photoemission spectroscopy study of the antiferromagnetic Kondo lattice $\mathrm{Ce}{\mathrm{Pd}}_{5}{\mathrm{Al}}_{2}$, focusing on the quasi-two-dimensional $k$-space nature of its Fermi surface and, tuning photon energy to the Ce $4d--4f$ on-resonance transition, the hybridization of the Ce $4f$ state. A strong shoulder feature on the ${f}^{0}$ peak was detected, suggesting hybridization between conduction and $f$ bands. On-resonance spectra revealed narrow, yet hybridized quasiparticle bands with sharp peaks and $\ensuremath{\sim}$ 9 meV energy dispersion near the Fermi energy ${E}_{F}$. The observed dispersive hybridized $f$ band can be well described by a hybridization-band picture based on the periodic Anderson model (PAM). Hence, the $4f$ electrons in $\mathrm{Ce}{\mathrm{Pd}}_{5}{\mathrm{Al}}_{2}$ display a dual nature, with both localized and itinerant features, but with dominantly localized character.

We report the successful synthesis, crystal structure, and electrical properties of Sr

The underlying mechanism behind the metal-to-insulator transition in ${\mathrm{VO}}_{2}$ is still a topic of intense debate. The two leading theoretical interpretations associate the transition with either electron-lattice or electron-electron correlations. Novel experimental results are required to converge towards one of the two scenarios. Here we report on a temperature-dependent angle-resolved photoelectron study of ${\mathrm{VO}}_{2}$ thin films across the metal-to-insulator transition. The obtained experimental results are compared to density functional theory calculations. We find an overall energy shift and compression of the electronic band structure across the transition while the overall band topology is conserved. The results demonstrate the importance of electron-electron correlations in establishing the insulating state.

Nature Communications 12(1), 3197 (2021). doi:10.1038/s41467-021-23435-y, The quantum Hall effect (QHE) is traditionally considered to be a purely two-dimensional (2D) phenomenon. Recently, however, a three-dimensional (3D) version of the QHE was reported in the Dirac semimetal ZrTe$_5$. It was proposed to arise from a magnetic-field-driven Fermi surface instability, transforming the original 3D electron system into a stack of 2D sheets. Here, we report thermodynamic, spectroscopic, thermoelectric and charge transport measurements on such ZrTe$_5$samples. The measured properties: magnetization, ultrasound propagation, scanning tunneling spectroscopy, and Raman spectroscopy, show no signatures of a Fermi surface instability, consistent with in-field single crystal X-ray diffraction. Instead, a direct comparison of the experimental data with linear response calculations based on an effective 3D Dirac Hamiltonian suggests that the quasi-quantization of the observed Hall response emerges from the interplay of the intrinsic properties of the ZrTe$_5$ electronic structure and its Dirac-type semi-metallic character., Published by Nature Publishing Group UK, [London]

We present a combined oxygen $K$-edge x-ray absorption spectroscopy and resonant inelastic x-ray scattering (RIXS) study of the bilayer ruthenate ${\mathrm{Ca}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$. Our RIXS experiments on ${\mathrm{Ca}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$ were carried out on the overlapping planar and interplanar oxygen resonances, which are distinguishable from the apical one. Comparison to equivalent oxygen $K$-edge spectra recorded on band-Mott insulating ${\mathrm{Ca}}_{2}\mathrm{Ru}{\mathrm{O}}_{4}$ is made. In contrast to ${\mathrm{Ca}}_{2}\mathrm{Ru}{\mathrm{O}}_{4}$ spectra, which contain excitations linked to Mott physics, ${\mathrm{Ca}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$ spectra feature only intra-${t}_{2g}$ ones that do not directly involve the Coulomb energy scale. As found in ${\mathrm{Ca}}_{2}\mathrm{Ru}{\mathrm{O}}_{4}$, we resolve two intra-${t}_{2g}$ excitations in ${\mathrm{Ca}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$. Moreover, the lowest lying excitation in ${\mathrm{Ca}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$ shows a significant dispersion, revealing a collective character different from what is observed in ${\mathrm{Ca}}_{2}\mathrm{Ru}{\mathrm{O}}_{4}$. Theoretical modeling supports the interpretation of this lowest energy excitation in ${\mathrm{Ca}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$ as a magnetic transverse mode with multiparticle character, whereas the corresponding excitation in ${\mathrm{Ca}}_{2}\mathrm{Ru}{\mathrm{O}}_{4}$ is assigned to combined longitudinal and transverse spin modes. These fundamental differences are discussed in terms of the inequivalent magnetic ground-state manifestations in ${\mathrm{Ca}}_{2}\mathrm{Ru}{\mathrm{O}}_{4}$ and ${\mathrm{Ca}}_{3}{\mathrm{Ru}}_{2}{\mathrm{O}}_{7}$.

Since the discovery of graphene, intensive efforts have been made in search of novel two-dimensional (2D) materials. Decreasing the materials dimensionality to their ultimate thinness is a promising route to unveil new physical phenomena, and potentially improve the performance of devices. Among recent 2D materials, analogs of graphene, the group IV elements have attracted much attention for their unexpected and tunable physical properties. Depending on the growth conditions and substrates, several structures of silicene, germanene, and stanene can be formed. Here, we report the synthesis of a Kagome lattice of silicene on aluminum (111) substrates. We provide evidence of such an exotic 2D Si allotrope through scanning tunneling microscopy (STM) observations, high-resolution core-level (CL) and angle-resolved photoelectron spectroscopy (ARPES) measurements, along with Density Functional Theory calculations., 13 pages, 6 figures

The authors study a charge-orbital-spin correlation of high-pressure synthesized quasi-one-dimensional NaMn${}_{2}$O${}_{4}$ and Li${}_{0.92}$Mn${}_{2}$O${}_{4}$ using a low-temperature neutron powder diffraction.

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$$^+$$ + ) 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 ($$\mu ^+$$ μ + 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$$^+$$ + dynamics in honeycomb layered oxide material $${\hbox {K}_2\hbox {Ni}_2\hbox {TeO}_6}$$ K 2 Ni 2 TeO 6 using mainly the $$\mu ^+$$ μ + SR technique. Our low-temperature $$\mu ^+$$ μ + SR results together with complementary magnetic susceptibility measurements find an antiferromagnetic transition at $$T_{\mathrm{N}}\approx 27$$ T N ≈ 27 K. Further $${\mu}^{+}$$ μ + SR studies performed at higher temperatures reveal that potassium ions (K$$^+$$ + ) become mobile above 200 K and the activation energy for the diffusion process is obtained as $$E_{\mathrm{a}}=121 (13)$$ E a = 121 ( 13 ) meV. This is the first time that K$$^+$$ + dynamics in potassium-based battery materials has been measured using $$\mu ^+$$ μ + 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.

Phase transitions have been surmised as underlying factors behind the exceptional electrochemical, ionic and magnetic functionalities that have catapulted honeycomb layered oxides as superb functional materials. As such, in this study (short communication), we explore temperature elevation as an avenue for inducing phase transitions in honeycomb layered oxides adopting the composition A2M2TeO6 (A = Li, Na, K; M = (transition) metal). X-ray diffraction analyses indicate structural changes occurring in Na2Ni2TeO6 hexagonal lattice (centrosymmetric P63/mcm → accentric P63(22) space group) with increase in temperature, whilst in the potassium homologue (K2Ni2TeO6), the phase transitions entail multiple changes in the lattice (from the initial hexagonal → monoclinic (pseudo-orthorhombic) lattice at intermediate temperatures) which reverts back to its initial hexagonal lattice with further increase in temperatures. This study opens an alternative channel for generating phase transition beside electrochemical alkali (re)insertion.

Natural abundance, impressive chemical characteristics and economic feasibility have rekindled the appeal for rechargeable sodium (Na) batteries as a practical solution for the growing energy demand, environmental sustainability and energy independence. However, the scarcity of viable positive electrode materials remains a huge impediment to the actualization of this technology. In this paper, we explore honeycomb layered oxides adopting the composition Na$_2$Ni$_{2-x}$Co$_x$TeO$_6$ ($x = 0, 0.25$ and $0.50$) as feasible positive electrode (cathode) materials for rechargeable sodium batteries at both room- and elevated temperatures using ionic liquids. Through standard galvanostatic assessments and analyses we demonstrate that substitution of nickel with cobalt in Na$_2$Ni$_2$TeO$_6$ leads to an increase in the discharge voltage to nearly $4$ V (versus Na$^+$ / Na) for the Na$_2$Ni$_{2-x}$Co$_x$TeO$_6$ family of honeycomb layered oxide materials, which surpasses the attained average voltages for most layered oxide positive electrode materials that facilitate Na-ion desertion. We also verify the increased kinetics within the Na$_2$Ni$_{2-x}$Co$_x$TeO$_6$ honeycomb layered oxides during operations at elevated temperatures which lead to an increase in reversible capacity of the rechargeable Na battery. This study underpins the doping of congener transition metal atoms to the honeycomb structure of Na$_2$Ni$_2$TeO$_6$ in addition to elevated-temperature operation as a judicious route to enhance the electrochemical performance of analogous layered oxides., 16 pages, 4 figures, 1 cover art (Electronic Supplementary Information: 10 pages, 5 figures, 3 tables)

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\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}+) 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 (\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\mu ^+$$\end{document}μ+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\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}+ dynamics in honeycomb layered oxide material \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\hbox {K}_2\hbox {Ni}_2\hbox {TeO}_6}$$\end{document}K2Ni2TeO6 using mainly the \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\mu ^+$$\end{document}μ+SR technique. Our low-temperature \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\mu ^+$$\end{document}μ+SR results together with complementary magnetic susceptibility measurements find an antiferromagnetic transition at \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$T_{\mathrm{N}}\approx 27$$\end{document}TN≈27 K. Further \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\mu}^{+}$$\end{document}μ+SR studies performed at higher temperatures reveal that potassium ions (K\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}+) become mobile above 200 K and the activation energy for the diffusion process is obtained as \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$E_{\mathrm{a}}=121 (13)$$\end{document}Ea=121(13) meV. This is the first time that K\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}+ dynamics in potassium-based battery materials has been measured using \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\mu ^+$$\end{document}μ+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.

Proper characterisation of investigated samples is vital when studying superconductivity as impurities and doping inhomogeneities can affect the physical properties of the measured system. We present a method where a polarised neutron imaging setup utilises the precession of spin-polarised neutrons in the presence of a trapped field in the superconducting sample to spatially map out the critical temperature for the phase transition between superconducting and non-superconducting states. We demonstrate this method on a superconducting crystal of the prototypical high-temperature superconductor (La,Sr)$_2$CuO$_4$. The results, which are backed up by complementary magnetic susceptibility measurements, show that the method is able to resolve minor variations in the transition temperature across the length of the LSCO crystal, caused by inhomogeneities in strontium doping., 11 pages, 7 figures

We use resonant inelastic x-ray scattering to investigate charge-stripe correlations in La_{1.675}Eu_{0.2}Sr_{0.125}CuO_{4}. By differentiating elastic from inelastic scattering, it is demonstrated that charge-stripe correlations precede both the structural low-temperature tetragonal phase and the transport-defined pseudogap onset. The scattering peak amplitude from charge stripes decays approximately as T^{-2} towards our detection limit. The in-plane integrated intensity, however, remains roughly temperature independent. Therefore, although the incommensurability shows a remarkably large increase at high temperature, our results are interpreted via a single scattering constituent. In fact, direct comparison to other stripe-ordered compounds (La_{1.875}Ba_{0.125}CuO_{4}, La_{1.475}Nd_{0.4}Sr_{0.125}CuO_{4}, and La_{1.875}Sr_{0.125}CuO_{4}) suggests a roughly constant integrated scattering intensity across all these compounds. Our results therefore provide a unifying picture for the charge-stripe ordering in La-based cuprates. As charge correlations in La_{1.675}Eu_{0.2}Sr_{0.125}CuO_{4} extend beyond the low-temperature tetragonal and pseudogap phase, their emergence heralds a spontaneous symmetry breaking in this compound.

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.

Angle-resolved photoelectron spectroscopy has been used to follow the valence band and near Fermi edge electronic band structure in the quasi-1D compound NaV 2 O 4 . In this current study we have acquired the very first high-quality, high-resolution ARPES data from this material. Our data clearly reveal two distinct dispersive bands that cross the Fermi level at different k F . This is a clear signature that the electronic properties of this material is affected by the presence of a mixed valence state on the different vanadium chains and possibly also the low-temperature magnetic spin order.

We systemically investigate the nature of Ce 4f electrons in structurally layered heavy-fermion compounds CcmMnIn3m+2n (with M =Co, Rh, Ir, and Pt, m=l, 2, n=0 - 2), at low temperature using on-resonance angle-resolved photoemission spectroscopy. Three heavy quasiparticle bands f^0, f^1_7/2 and f^1_5/2 are observed in all compounds, but their intensities and energy locations vary greatly with materials. The strong f^0 states imply that the localized electron behavior dominates the Ce 4f states. The Ce 4f electrons are partially hybridized with the conduction electrons, making them have the dual nature of localization and itinerant. Our quantitative comparison reveals that the f^1_5/2 / f^0 intensity ratio is more suitable to reflect the 4f-state hybridization strength., Comment: 7 pages, 4 figures

We use high-resolution angle-resolved photoemission spectroscopy to investigate the electronic structure of the antiferromagnetic heavy fermion compound CePt2In7, which is amember of the CeIn3-deri ...

A comprehensive angle-resolved photoemission spectroscopy study of the band structure in single-layer cuprates is presented with the aim of uncovering universal trends across different materials. Five different hole- and electron-overdoped cuprate superconductors (${\mathrm{La}}_{1.59}{\mathrm{Eu}}_{0.2}{\mathrm{Sr}}_{0.21}{\mathrm{CuO}}_{4}$, ${\mathrm{La}}_{1.77}{\mathrm{Sr}}_{0.23}{\mathrm{CuO}}_{4}$, ${\mathrm{Bi}}_{1.74}{\mathrm{Pb}}_{0.38}{\mathrm{Sr}}_{1.88}{\mathrm{CuO}}_{6+{\delta}}$, ${\mathrm{Tl}}_{2}{\mathrm{Ba}}_{2}{\mathrm{CuO}}_{6+{\delta}}$, and ${\mathrm{Pr}}_{1.15}{\mathrm{La}}_{0.7}{\mathrm{Ce}}_{0.15}{\mathrm{CuO}}_{4}$) have been studied with special focus on the bands with a predominately $d$-orbital character. Using a light polarization analysis, the ${e}_{g}$ and ${t}_{2g}$ bands are identified across these materials. A clear correlation between the ${d}_{3{z}^{2}{-}{r}^{2}}$ band energy and the apical oxygen distance ${d}_{\mathrm{A}}$ is demonstrated. Moreover, the compound dependence of the ${d}_{{x}^{2}{-}{y}^{2}}$ band bottom and the ${t}_{2g}$ band top is revealed. A direct comparison to density functional theory (DFT) calculations employing hybrid exchange-correlation functionals demonstrates excellent agreement. We thus conclude that the DFT methodology can be used to describe the global band structure of overdoped single-layer cuprates on both the hole- and electron-doped side." name="description" />

Anomalous successive structural transitions in layered 1

We present a comprehensive angle-resolved photoemission spectroscopy study of Ca1.8Sr0.2RuO4. Four distinct bands are revealed and along the Ru-O bond direction their orbital characters are identif ...

The temperature dependent dehydrogenation of naphthalene on Ni(111) has been investigated using vibrational sum-frequency generation spectroscopy, X-ray photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory with the aim of discerning the reaction mechanism and the intermediates on the surface. At 110 K, multiple layers of naphthalene adsorb on Ni(111); the first layer is a flat lying chemisorbed monolayer, whereas the next layer(s) consist of physisorbed naphthalene. The aromaticity of the carbon rings in the first layer is reduced due to bonding to the surface Ni-atoms. Heating at 200 K causes desorption of the multilayers. At 360 K, the chemisorbed naphthalene monolayer starts dehydrogenating and the geometry of the molecules changes as the dehydrogenated carbon atoms coordinate to the nickel surface; thus, the molecule tilts with respect to the surface, recovering some of its original aromaticity. This effect peaks at 400 K and coincides with hydrogen desorption. Increasing the temperature leads to further dehydrogenation and production of H-2 gas, as well as the formation of carbidic and graphitic surface carbon. Published under license by AIP Publishing.