Context. Modified Newtonian dynamics (MOND) is a promising alternative to dark matter. To further test the theory, there is a need for fluid- and particle-dynamics simulations. The force in MOND is not a direct particle-particle interaction, but derives from a potential for which a nonlinear partial differential equation (PDE) needs to be solved. Normally, this makes the problem of simulating dynamical evolution computationally expensive. Aims. We intend to develop a fast particle-mesh (PM) code for MOND (the AQUAL formalism). Methods. We transformed the nonlinear equation for MOND into a system of linear PDEs plus one algebraic equation. An iterative scheme with the fast Fourier transform (FFT) produces successively better numerical approximations. Results. The algorithm was tested for dynamical systems in MOND where analytical solutions are known: the two-body problem, a body with a circular ring, and a spherical distribution of particles in thermal equilibrium in the self-consistent potential. Conclusions. The PM code can accurately calculate the forces at subpixel scale and reproduces the analytical solutions. Four iterations are required for the potential, but when the spatial steps are small compared to the kernel width, one iteration is suffices. The use of a smoothing kernel for the accelerations is inevitable in order to eliminate the self-gravity of the point particles. Our PDE solver is 15 to 42 times as slow as a standard Poisson solver. However, the smoothing and particle propagation takes up most of the time above one particle per 10 ³ pixels. The FFTs, the smoothing, and the propagation part in the code can all be parallelized.

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Rare-Earth oxyhydrides (REH3-2xOx) are characterized by photodarkening when illuminated by photons having an energy exceeding that of the band gap. We propose that the film is segregated in hydrogen rich and hydrogen poor areas. Upon illumination, the excited electrons reduce the three-valent cations inducing an insulator to metal transition in the hydrogen rich entities. These small metallic oxyhydride clusters are responsible for the enhanced optical absorption. In the surrounding semiconductor matrix the photoexcitation induces a transition from p to n-type conductivity. This persistent photoconductivity is due to trapping of the holes by hydride ions. As a result, the Fermi level rises above the conduction band inducing a Burstein-Moss effect and a large increase in the conductivity.@en

Cycling stability of the photochromic effect in rare-earth oxyhydride thin films is of great importance for long-term applications such as smart windows. However, an increasingly slower bleaching rate upon photochromic cycling was found in yttrium oxyhydride thin films; the origin of this memory effect is yet unclear. In this work, the microstructural changes under six photodarkening-bleaching cycles in YHxOy and GdHxOy thin films are investigated by in situ illumination Doppler broadening positron annihilation spectroscopy, complemented by positron annihilation lifetime spectroscopy (PALS) investigations on YHxOy films before and after one cycle. For the first three cycles, the Doppler broadening S parameter after bleaching increases systematically with photodarkening-bleaching cycle, and correlates with the bleaching time constant extracted from optical transmittance measurements. This suggests that the microstructural evolution that leads to progressively slower bleaching involves vacancy creation and agglomeration. PALS suggests that during a photodarkening-bleaching cycle, divacancies are formed that are possibly composed of illumination-induced hydrogen vacancies and preexisting yttrium monovacancies, and vacancy clusters grow, which might be due to local removal of hydrogen. If bleaching is a diffusion-related process, the formed vacancy defects induced by illumination might affect the diffusion time by reducing the diffusion coefficient. Hydrogen loss could also be a key factor in the reduced bleaching kinetics. Other microstructural origins including domain growth, or formation of OH- hydroxide groups, are also discussed with respect to the slower bleaching kinetics. During the fourth to sixth photodarkening-bleaching cycle, reversible shifts in the Doppler S and W parameters are seen that are consistent with the reversible formation of metallic-like domains, previously proposed as a key factor in the mechanism for the photochromic effect.

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Recently, the all-d-metal Ni(Co)MnTi based Heusler compounds are found to have a giant magnetocaloric effect (GMCE) near room temperature and manifest different functionalities like multicaloric effects, which can be employed for solid-state refrigeration. However, in comparison to other traditional Heusler compounds, the relatively large thermal hysteresis (ΔT_hys) and moderately steep ferromagnetic phase transition provides limitations for real applications. Here, we present that fast solidification (suction casting) can sufficiently tailor the GMCE performance by modifying the microstructure. Compared with the arc-melted sample, the magnetic entropy change of the suction-casted sample shows a 67% improvement from 18.4 to 29.4 Jkg⁻¹K⁻¹ for a field change (∆μ₀H) of 5 T. As the thermal hysteresis has maintained a low ΔT_hys value (5.5 K) for the enhanced first-order phase transition, a very competitive reversible magnetic entropy change of 21.8 Jkg⁻¹K⁻¹ for ∆μ₀H = 5 T is obtained. Combining high-resolution transmission electron microscopy (HRTEM) and positron annihilation spectroscopy (PAS) results, the difference in lattice defect concentration is found to be responsible for the significant improvement in GMCE for the suction-cast sample, which suggests that defect engineering can be applied to control the GMCE. Our study reveals that fast solidification can effectively regulate the magnetocaloric properties of all-d-metal NiCoMnTi Heusler compounds without sacrificing ΔT_hys.

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Rare earth oxyhydrides REO_xH_(3-2x), with RE = Y, Sc, or Gd and a cationic FCC lattice, are reversibly photochromic in nature. It is known that structural details and anion (O^2-:H^-) composition dictate the efficiency of the photochromic behavior. The mechanism behind the photochromism is, however, not yet understood. In this study, we use ¹H, ²H, ¹⁷O, and ⁸⁹Y solid-state NMR spectroscopy and density functional theory (DFT) calculations to study the various yttrium, hydrogen, and oxygen local environments, anion oxidation states, and hydride ion dynamics. DFT models of YO_xH_(3-2x) with both anion-ordered and anion-disordered sublattices are constructed for a range of compositions and show a good correlation with the experimental NMR parameters. Two-dimensional ¹⁷O-¹H and ⁸⁹Y-¹H NMR correlation experiments reveal heterogeneities in the samples, which appear to consist of hydride-rich (x ≈ 0.25) and hydride-poor domains (x ≈ 1) rather than a single composition with homogeneous anion mixing. The compositional variation (as indicated by the different x values in YO_xH_(3-2x)) is determined by comparing static ¹H NMR line widths with calculated ¹H-¹H dipolar couplings of yttrium oxyhydride models. The 1D ¹⁷O MAS spectrum demonstrates the presence of a small percentage of hydroxide (OH^-) ions. DFT modeling indicates a reaction between the protons of hydroxides and hydrides to form molecular hydrogen (H⁺ + H^- → H₂). ¹H MAS NMR indicates the presence of a mobile component that, based on this finding, is attributed to trapped molecular H₂ in the lattice.

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Rare-earth (RE) oxyhydride thin films show a color-neutral, reversible photochromic effect at ambient conditions. The origin of the photochromism is the topic of current investigations. Here, we investigated the lattice defects, electronic structure, and crystal structure of photochromic YHxOy and GdHxOy thin films deposited by magnetron sputtering using positron annihilation techniques and X-ray diffraction, in comparison with Y, YH∼1.9, Y2O3, Gd, GdH∼1.8, and Gd2O3 films. Positron annihilation lifetime spectroscopy (PALS) reveals the presence of cation monovacancies in the as-deposited Y and YH∼1.9 films at concentrations of ∼10-5 per cation. In addition, vacancy clusters and nanopores are found in the as-prepared YHxOy and Y2O3 films. Doppler broadening positron annihilation spectroscopy (DB-PAS) of the Y- A nd Gd-based films reflects the transition from a metallic to an insulating nature of the RE metal, metal hydride, semiconducting oxyhydride and insulating oxide films. In-situ illumination DB-PAS shows the irreversible formation predominantly of di-vacancies, as PALS showed that cation mono-vacancies are already abundantly present in the as-prepared films. The formation of di-vacancies supports conjectures that H-(and/or O2-) ions become mobile upon illumination, as these will leave anion vacancies behind, some of which may subsequently cluster with cation vacancies present. In addition, in RE oxyhydride films, partially reversible shifts in the Doppler parameters are observed that correlate with the photochromic effect and point to the formation of metallic domains in the semiconducting films. Two processes are discussed that may explain the formation of these metallic domains and the changes in optical properties associated with the photochromic effect. The first process considers the reversible formation of metallic nanodomains with reduced O: H composition by transport of light-induced mobile hydrogen and local oxygen displacements. The second process considers metallic nanodomains resulting from the trapping of photoexcited electrons in an eg orbital at the yttrium ions surrounding positively charged hydrogen vacancies that are formed by light-induced removal of hydrogen atoms from octahedral sites. When a sufficiently large concentration, on the order of ∼10%, is reached in a certain domain of the film, band formation of the eg electrons may occur, leading to an Anderson-Mott insulator-metal transition like the case of yttrium trihydride in these domains.

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In this paper, we investigate by ab initio DFT how the O:H ratio influences the formation and lattice energy, metastability, and optical properties of Y and La anion-disordered ROxH3-2x oxyhydrides. To achieve this, a set of special quasirandom structures (SQS) is introduced to model anion-disorder along the whole RH3-R2O3 composition line. A comparison with an extensive set of anion-ordered polymorphs of the same composition shows the comparable energy of the anion-disordered phase, which, in particular, in the H-rich composition interval showed the lowest relative energy. In turn, the metastability of the anion-disordered phase depends on the cation size (Y versus La), which determines the maximum H content above which the CaF2-type structure itself becomes unstable. To overcome the accuracy limitations of classical DFT, the modified Becke-Johnson (mBJ) scheme is employed in the study of the electronic properties. We show that major differences occur between H-rich and O-rich R oxyhydrides, as the octahedral H- present for x<1 form electronic states at the top of the valence band, which reduce the energy band gap and dominate the electronic transitions at lower energies, thus increasing the refractive index of the material in the VIS-nIR spectral range. Comparing the DFT results to experimental data on photochromic Y oxyhydride films reinforces the hypothesis of anion-disorder in the H-rich films (x<1), while it hints towards some degree of anion ordering in the O-rich ones (x>1). Our paper exemplifies a strategy to calculate ab initio the electronic/optical properties of a wide range of materials with occupational disorder.

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To develop an understanding of the photochromic effect in rare-earth metal oxyhydride thin films (REH3-2xOx, here RE = Y), we explore the aliovalent doping of the RE cation. We prepared Ca-doped yttrium oxyhydride thin films ((CazY1-z)HxOy) by reactive magnetron cosputtering with Ca doping concentrations between 0 and 36 at. %. All of the films are semiconductors with a constant optical band gap for Ca content below 15%, while the band gap expands for compositions above 15%. Ca doping affects the photochromic properties, resulting in (1) a lower photochromic contrast, likely due to a lower H- concentration, and (2) a faster bleaching speed, caused by a higher pre-exponential factor. Overall, these results point to the importance of the H- concentration for the formation of a "darkened"phase and the local rearrangement of these H- for the kinetics of the process.

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Reduction-oxidation (redox) reactions that transfer conduction electrons from the anode to the cathode are the fundamental processes responsible for generating power in Li-ion batteries. Electronic and microstructural features of the cathode material are controlled by the nature of the redox orbitals and how they respond to Li intercalation. Thus, redox orbitals play a key role in performance of the battery and its degradation with cycling. We unravel spectroscopic descriptors that can be used to gain an atomic-scale handle on the redox mechanisms underlying Li-ion batteries. Our focus is on X-ray Compton Scattering and Positron Annihilation spectroscopies and the related computational approaches for the purpose of identifying orbitals involved in electrochemical transformations in the cathode. This review provides insight into the workings of lithium-ion batteries and opens a pathway for rational design of next-generation battery materials.

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The energy axes of the RBS and ERD data (contained in Figures 2a,b,d,e, and S4) were originally underestimated, and the corrected figures appear below and in the Supporting Information. The change is in the conversion from raw data to the energy scale, which was initially converted incorrectly. The rescaled x-axis does not change the data conclusions since the assignment of peaks to atoms remains the same and the intensity of the peaks is unaffected. Hence, it has no influence on the calculations and conclusions in the original text. (Figure presented).

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Thin films of rare-earth metal oxyhydrides, such as yttrium oxyhydrides (YH3-2xOx), show a photochromic effect where the transparency of the films decreases reversibly upon exposure to UV light. However, the exact mechanism behind this effect is unknown. In this paper, we describe the behavior of YH3-2xOx thin films, with different O2-:H- ratios, under dark and illuminated conditions using in situ muon spin relaxation (μ+SR), and compare that to an oxygen-free reference compound, yttrium dihydride (YH2-δ). The muon acts as a local magnetic probe in our compounds, giving information related to electronic, structural, and photochromic properties. Although YH2-δ is the parent compound to YH3-2xOx, the muon behavior in these two materials is different - the muon electrostatically interacts primarily with H- (dihydride) or O2- (oxyhydride) - leading to the use of different theoretical models. For YH2-δ, we observed the formation of an entangled H-μ complex and the onset of Mu+ diffusion and H- rearrangement above 150 K (EA,Γ=67±13meV). For the oxyhydrides, we adopted a transition state model, where Mu0 formation and gradual Mu+ recovery take place, accompanied by the formation of a Mu+-O2- complex and a polaron at the Y cation. The activation energy (EA,dia) associated with Mu+ recovery is dependent on lattice relaxation and is lower for thin films of higher H content (EA,dia=29-45meV). In situ illumination further reduces this energy barrier for all measured oxyhydrides, suggesting that the photochromic effect involves a reversible structural rearrangement during photodarkening.

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Rare-earth oxyhydride REOxH3-2x thin films prepared by air-oxidation of reactively sputtered REH2 dihydrides show a color-neutral, reversible photochromic effect at ambient conditions. The present work shows that the O/H anion ratio, as well as the choice of the cation, allow to largely tune the extent of the optical change and its speed. The bleaching time, in particular, can be reduced by an order of magnitude by increasing the O/H ratio, indirectly defined by the deposition pressure of the parent REH2. The influence of the cation (RE = Sc, Y, Gd) under comparable deposition conditions is discussed. Our data suggest that REs of a larger ionic radius form oxyhydrides with a larger optical contrast and faster bleaching speed, hinting to a dependency of the photochromic mechanism on the anion site-hopping.

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In high-efficiency silicon solar cells featuring carrier-selective passivating contacts based on ultrathin SiOx/poly-Si, the appropriate implementation of transparent conductive oxide (TCO) layers is of vital importance. Considerable deterioration in passivation quality occurs for thin poly-Si-based devices owing to the sputtering damage during TCO deposition. Curing treatment at temperatures above 350 °C can recover such degradation, whereas the opto-electrical properties of the TCO are affected as well, and the carrier transport at the poly-Si/TCO contact is widely reported to degrade severely in such a procedure. Here, we propose straightforward approaches, post-deposition annealing at 400 °C in nitrogen, hydrogen, or air ambience, are proposed to tailor material properties of high-mobility hydrogenated fluorine-doped indium oxide (IFO:H) film. Structural, morphological, and opto-electrical properties of the IFO:H films are investigated as well as their inherent electron scattering and doping mechanisms. Hydrogen annealing treatment proves to be the most promising strategy. The resulting layer exhibits both optimal opto-electrical properties (carrier density = 1.5 × 1020 cm-3, electron mobility = 108 cm2 V-1 s-1, and resistivity = 3.9 × 10-4 ω cm) and remarkably low contact resistivities (∼20 mω cm2 for both n- and p-contacts) in poly-Si solar cells. Even though the presented cells are limited by the metallization step, the obtained IFO:H-base solar cell show an efficiency improvement from 20.1 to 20.6% after specific hydrogen treatment, demonstrating the potential of material manipulation and contact engineering strategy in high-efficiency photovoltaic devices endowed with TCOs.

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Doppler broadening positron annihilation spectroscopy depth profiles were collected on photochromic YO_xH_y thin films. In situ UV illumination of photochromic semiconductor YO_xH_y films leads to an increase in S-parameter and a large reduction in W-parameter, possibly caused by a change in the charge state of vacancies or the growth of hydrogen-rich metallic Y(O_x)H_y clusters, albeit that vacancy formation or changes in positronium formation during illumination might also play a role. Intriguingly, both the S- and W-parameters increase during thermal bleaching, indicating that another process takes place. The Doppler parameters do not return to their initial values after complete thermal bleaching, suggesting that persistent local rearrangements of vacancies and possibly hydride ions have occurred during the full photodarkening-thermal bleaching cycle. Positron annihilation lifetime spectroscopy shows that a small fraction of positronium is formed in as-deposited YO_xH_y films, indicating that the films contain some nanopores.

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A new method is developed to produce mesoporous titania thin films at room temperature using the enzyme papain in a dip-coating procedure, providing low-cost titania films in a sustainable manner. Quartz crystal microbalance, positron annihilation Doppler broadening and lifetime spectroscopy, scanning electron microscopy, and X-ray diffraction are used to determine the deposition and structural properties of the films. As-deposited films have low densities ρ ≈ 0.6 g cm⁻³, contain small micropores and proteins, and exhibit corrugated surfaces. Annealing at temperatures of 300 °C or higher leads to the destruction and evaporation of most of the organic material, resulting in a thickness decrease of 50–60%, more pure titania films with increased density, an increase in micropore size and a decrease in the concentration and size of atomic-scale vacancies. Up to 50 layers could be stacked, allowing easy control over the total layer thickness. Based on these titania films, first test devices consisting of natural dye-sensitized solar cells are produced, that show photovoltaic activity and indicate possibilities for low-cost, accessible, organic production of solar cells. Given the wide range of other applications for titania, this new method is a promising candidate for improving the fabrication of those products with respect to cost, sustainability, and production speed.

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Barium di-silicide (BaSi₂) is a very promising absorber material for high-efficiency thin-film solar cells, due to its suitable bandgap, high light absorption coefficient, and long minority-carrier lifetime. In this study, we compare the nanostructure, layer composition, and point defects of BaSi₂ thin films deposited by Radio Frequency (RF) sputtering, Thermal Evaporation (TE), and Molecular Beam Epitaxy (MBE), using Doppler Broadening Positron Annihilation Spectroscopy (DB-PAS) depth profiling, Raman spectroscopy, and x-ray diffraction. Our DB-PAS study on thermally annealed RF-sputter deposited and on TE-deposited BaSi₂ layers, in a comparison with high quality BaSi₂ films produced by MBE, points to the presence of vacancy-oxygen complexes and Si or Ba mono-vacancies, respectively, in the (poly)crystalline BaSi₂ films. The degree of near-surface oxidation increases, going from MBE and TE to the industrially applicable RF-sputtered deposition synthesis. The use of a-Si capping layers on the thermally annealed RF-sputtered BaSi₂ films leads to a clear reduction in sub-surface oxidation and improves the quality of the BaSi₂ films, as judged from DB-PAS.

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The degradation of hybrid perovskite films when exposed to ambient air is a major challenge for the development of perovskite-based photovoltaics at large scale. At present, little is known about the environmental degradation of perovskite films associated with the development of structural defects or open volumes (such as atomic vacancies, voids, crystallographic defects and grain boundary defects) in the lattice, and about the depth dependence of the structural degradation. Therefore, in this work, we use Doppler broadening-positron annihilation spectroscopy (DB-PAS) depth-profiling to gain insight into the structural degradation of CH ₃ NH ₃ PbI _3-x Cl _x perovskite when exposed to ambient air. In parallel, we investigate the effect of ultrathin (<1 nm) atomic layer deposited (ALD) Al ₂ O ₃ processed directly on top of the perovskite as a means to suppress the degradation process. Specifically, we infer that the perovskite degradation involves changes in open volumes in its crystal lattice. This could be caused by the ingress of H ₂ O molecules into the cation vacancies. In parallel, chemical changes in the perovskite films upon decomposition are observed, accompanied by a decrease in the film thickness as a function of air exposure time. When the perovskite films are decorated with ALD Al ₂ O ₃ , the latter delays the thickness reduction of the perovskite layer during air exposure and also suppresses the changes in its open volumes and chemical transformations. Our findings illustrate that an improved understanding of the perovskite degradation process can be obtained using DB-PAS, especially when combined with other thin film characterization techniques, such as X-ray diffraction and X-ray photoelectron spectroscopy.

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Positron annihilation lifetime spectroscopy (PALS) and Doppler broadening positron annihilation spectroscopy (DB-PAS) depth profiling demonstrate pronounced growth of vacancy clusters at the grain boundaries of as-deposited Al-doped ZnO films deposited as transparent conductive oxide (TCO) on Cu(In,Ga)Se2 (CIGS) solar cells upon accelerated degradation at 85∘C/85% relative humidity. Quantitative fractions of positrons trapped either in the vacancy clusters at the grain boundaries or in Zn monovacancies inside the grains of ZnO:Al were obtained by detailed analysis of the PALS data using a positron trapping model. The time and depth dependence of the positron Doppler depth profiles can be accurately described using a planar diffusion model, with an extracted diffusion coefficient of 35nm2/hour characteristic for in-diffusion of molecules such as H2O and CO2 into ZnO:Al TCO films via the grain boundaries, where they react with the ZnO:Al. This leads to increased open volume at the grain boundaries that imposes additional transport barriers and may lead to charge carrier trapping and nonradiative recombination. Simultaneously, a pronounced increase in series resistance and a strong reduction in efficiency of the ZnO:Al capped CIGS solar cells is observed on a remarkably similar timescale. This strongly indicates that these atomic-scale processes of molecular in-diffusion and creation of open volume at the grain boundaries play a key role in the degradation of the solar cells.@en

Positron annihilation depth-profiling is used as an innovative tool to monitor the evolution of vacancy defects in two series of ZnO:Al transparent conductive oxide (TCO) layers for Cu(In,Ga)Se2 (CIGS) solar cells under accelerated degradation at 85??C/85% relative humidity. The first series of ZnO:Al layers are deposited directly on flat glass substrates, leading to low densities of (extended) grain boundaries in the ZnO:Al. These ZnO:Al layers only show an increase in open volume upon degradation in the near-surface range. The second series of ZnO:Al layers are deposited on the more corrugated surface of CdS/CIGS/Mo solar cells, and show, on the other hand, a pronounced formation of open volume throughout the layer. Its depth-dependence is consistent with in-diffusion of molecules such as H2O and CO2 into the ZnO:Al layer via the grain boundaries, as primary driver for the degradation. The detected time-dependence of the growth of open volume at the grain boundaries in the ZnO:Al TCO layer matches the time scale of the observed reduction in solar cell efficiency and series resistance, suggesting that the generated open volume induces a significant barrier against charge carrier transport.@en

Previous studies have shown that positron-annihilation spectroscopy is a highly sensitive probe of the electronic structure and surface composition of ligand-capped semiconductor quantum dots (QDs) embedded in thin films. The nature of the associated positron state, however, whether the positron is confined inside the QDs or localized at their surfaces, has so far remained unresolved. Our positron-annihilation lifetime spectroscopy studies of CdSe QDs reveal the presence of a strong lifetime component in the narrow range of 358-371 ps, indicating abundant trapping and annihilation of positrons at the surfaces of the QDs. Furthermore, our ab initio calculations of the positron wave function and lifetime employing a recent formulation of the weighted density approximation demonstrate the presence of a positron surface state and predict positron lifetimes close to experimental values. Our study thus resolves the long-standing question regarding the nature of the positron state in semiconductor QDs and opens the way to extract quantitative information on surface composition and ligand-surface interactions of colloidal semiconductor QDs through highly sensitive positron-annihilation techniques.

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