Edge X-ray Absorption Near-edge Structure Research Articles

Understanding phosphorus mobilization mechanisms in acidic soil amended with calcium-silicon-magnesium-potassium fertilizer

Calcium-silicon-magnesium-potassium fertilizer (CSMP) is usually used as an amendment to counteract soil acidification caused by historical excessive nitrogen (N) applications. However, the impact of CSMP addition on phosphorus (P) mobilization in acidic soils and the related mechanisms are not fully understood. Specifically, a knowledge gap exists with regards to changes in soil extracellular enzymes that contribute to P release. Such a knowledge gap was investigated by an incubation study with four treatments: i) initial soil (Control), ii) urea (60 mg kg−1) addition (U); iii) CSMP (1%) addition (CSMP) and iv) urea (60 mg kg−1) and CSMP (1%) additions (U + CSMP). Phosphorus mobilization induced by different processes was distinguished by biologically based P extraction. The Langmuir equation, K edge X-ray absorption near-edge structure spectroscopy, and ecoenzyme vector analysis according to the extracellular enzyme activity stoichiometry were deployed to investigate soil P sorption intensity, precipitation species, and microbial-driven turnover of organophosphorus. Results showed that CaCl2 extractable P (or citric acid extractable P) content increased by 63.4% (or 39.2%) in the soil with CSMP addition, compared with the study control. The accelerated mobilization of aluminum (Al)/iron (Fe)-bound P after CSMP addition, indicated by the reduction of the sum of FePO4·2H2O and AlPO4 proportion, contributed to this increase. The decrease of P sorption capacity can also be responsible for it. The CSMP addition increased enzyme extractable P in the soil nearly 7-fold and mitigated the limitations of carbon (C) and P for soil microorganisms (indicated by the enzyme stoichiometry and ecoenzyme vector analysis), suggesting that microbial turnover processes also contribute to P mobilization in amended acidic soil. These findings indicate that the P mobilization in CSMP amended acidic soil not only attributed to both decreasing P sorption capacity and dissolving phosphate precipitation, but also to the increase of the microbial turnover of the organophosphorus pool.

Insights into the Complex Oxidation Behaviour of Aqueous H3PO3 through in Situ P K- Edge XANES

High-temperature electrolyte membrane fuel cells (HT-PEMFCs) using H3PO4-doped membranes are an enticing choice for electrochemical energy sources at elevated temperatures [1]. Yet, one of the challenges concerning these systems is the reduction of H3PO4 to lower valency phosphorus compounds, such as H3PO3, during operation [2,3,4]. H3PO3 can strongly adsorb on the Pt catalysts, hence poisoning it and thereby lowering the fuel cell performance [5,6]. Interestingly, the presence of Pt may, under certain conditions, catalyze the chemical (re-)oxidation of aqueous H3PO3 back to H3PO4, illustrating the complexity of the H3POx – Pt interaction. Therefore, to optimize the performance of HT-PEMFCs by rational design of the catalyst/electrolyte interface, further insight into H3PO3 oxidation behaviour and Pt/H3PO3 interaction under conditions relevant to HT-PEMFCs operation is required.In this study, in situ P K- edge XANES (x-ray absorption near edge structure) spectroscopy was conducted to shed light on the oxidation behaviour of aqueous H3PO3 by investigating the impact of (i) different temperatures (25°C vs 75°C), (ii) varying electrode roughness (flat planar Pt vs rough Pt black), (iii) different electrode potentials (open circuit potentials vs more positive potentials [+0.8, +0.9, and +1.0 VRHE]), and (iv) varying molar concentrations of H3PO3 (0.1 , 1 , and 5 mol dm-3). Initially, XANES coupled with electrochemical characterization (e.g. OCP, cyclic voltammetry) of the system was performed under different radiation doses (i.e.: photon fluxes, exposure time) to determine the effect of radiolysis and/or radiation damage during experiments that may lead to misinterpretations of XANES results. Under high radiation dose, we find evidence of H2 presence in the vicinity of the Pt electrode, likely generated by water radiolysis. We have developed experimental procedures to suppress these undesirable effects during the collection of the XANES data, enabling an accurate determination of H3PO3 oxidation behaviour and minimizing the radiolysis contribution to the process. It was found that higher temperature facilitates the oxidation of aqueous H3PO3 to H3PO4, presumably because H3PO3 exists in the thermodynamically preferred “active” pyramidal form at elevated temperatures, which is more prone to react with H2O, forming H3PO4 and H2. In aqueous H3PO3 solutions with higher H2O contents, also more pronounced oxidation of H3PO3 is observed, indicating that oxidation of H3PO3 to H3PO4 in aqueous solutions proceeds via the presence of H2O. The experiments using rough Pt black electrodes additionally hint at the observation of electrochemical oxidation of H3PO3 to H3PO4 during the application of positive potentials. This work provides insights into the underlying chemical processes that occur at conditions relevant for HT-PEMFCs operation and thus it paves the way for possible strategies to mitigate H3PO3 poisoning of the Pt electrode during operation.

Thorium speciation in ilmenite concentrates from the Mandena deposit, Madagascar: Implications for environmental remediation and thorium beneficiation

Placer ilmenite deposits are important sources for titanium dioxide production but are often radioactive due to elevated thorium and uranium contents, posing significant challenges to their upgrading and downstream commercial applications. In this contribution, we have investigated ilmenite concentrates containing 133 ppm Th and 12.8 ppm U from the Mandena deposit, Madagascar, using a wide range of analytical techniques: powder X-ray diffraction, electron microprobe analysis, quantitative evaluation of materials by scanning electron microscopy, inductively coupled plasma mass spectrometry, laser ablation inductively coupled plasma mass spectrometry, synchrotron X-ray absorption spectroscopy, microbeam synchrotron X-ray fluorescence mapping, and microbeam synchrotron Laue X-ray diffraction analysis. Our data show that monazite-(Ce), mainly as discrete grains, accounts for ∼55% of Th in the Mandena ilmenite concentrates. Thorianite hosting the remaining Th at ∼45% is revealed by synchrotron Th LIII edge X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses and is correlated with the degree of ilmenite alteration. These results suggest that thorianite probably formed from the alteration of ilmenite and precipitated on the surface of altered ilmenite. The presence of monazite-(Ce) and thorianite in the Mandena ilmenite concentrates is further supported by principal component analysis of trace elements. Our results suggest that combined magnetic separation and acid leaching are effective for reducing the Th (and U) abundances in the Mandena ilmenite concentrates, via the removal of Th-bearing minerals. These findings have important implications for both Th remediation and beneficiation. Moreover, the precipitation of thorianite on the surface of altered ilmenite is an effective method for attenuating the common radionuclide Th in surficial environments.

DFT + U Simulation of the X-ray Absorption Near-Edge Structure of Bulk UO2 and PuO2.

Hubbard U-corrected density functional theory within the periodic boundary condition model in the WIEN2k code is used to simulate the actinide LIII and O K edge X-ray absorption near-edge structure (XANES) for UO2 and PuO2. Spin-orbit coupling effects are included, as are possible excitonic effects using supercells with a core hole on one of the atoms. Our calculations yield spectra in excellent agreement with previous experiments and superior to previous simulations. Density of states analysis reveals the mechanism behind the XANES peaks: the main contribution to the U/Pu LIII edges comes from the U/Pu d states hybridized with O p states, while as expected, the O p states primarily determine the O K edges of both UO2 and PuO2. The O K edges also feature O p hybridizing with U/Pu d and f states in the low-energy region and with U/Pu s and p states for the higher-energy peaks.

Speciation and Reactivity Control of Cu-Oxo Clusters via Extraframework Al in Mordenite for Methane Oxidation.

The stoichiometric conversion of methane to methanol by Cu-exchanged zeolites can be brought to highest yields by the presence of extraframework Al and high CH4 chemical potentials. Combining theory and experiments, the differences in chemical reactivity of monometallic Cu-oxo and bimetallic Cu-Al-oxo nanoclusters stabilized in zeolite mordenite (MOR) are investigated. Cu-L3 edge X-ray absorption near-edge structure (XANES), infrared (IR), and ultraviolet-visible (UV-vis) spectroscopies, in combination with CH4 oxidation activity tests, support the presence of two types of active clusters in MOR and allow quantification of the relative proportions of each type in dependence of the Cu concentration. Ab initio molecular dynamics (MD) calculations and thermodynamic analyses indicate that the superior performance of materials enriched in Cu-Al-oxo clusters is related to the activity of two μ-oxo bridges in the cluster. Replacing H2O with ethanol in the product extraction step led to the formation of ethyl methyl ether, expanding this way the applicability of these materials for the activation and functionalization of CH4. We show that competition between different ion-exchanged metal-oxo structures during the synthesis of Cu-exchanged zeolites determines the formation of active species, and this provides guidelines for the synthesis of highly active materials for CH4 activation and functionalization.

Enhanced phosphorus fixation in red mud-amended acidic soil subjected to periodic flooding-drying and straw incorporation

Globally, red mud is a solid waste from the aluminum industry, which is rich in iron oxides. It is an effective soil amendment in agriculture that protects connected waters from legacy diffuse phosphorus (P) soil losses. However, other management practices such as flooding and drying and/or organic carbon inputs could potentially alter P fixation in these red mud-amended soils thereby releasing P to waters. The present study was designed and conducted to monitor the mobilization of P in a red mud-amended acidic soil subjected to periodic flooding-drying, straw incorporation, and a mix of both management practices. Sequential extraction and K edge X-ray absorption near-edge structure spectroscopy (k-XANES) were employed to distinguish P fractions/species and the Langmuir model was fitted to evaluate soil P sorption capacity. The content of labile P indicated by CaCl2–P was increased significantly by 101% and 28.7% in the straw incorporation and periodic flooding-drying treatments, while it decreased significantly by 22.3% in the combined periodic flooding-drying with straw incorporation treatment, compared with Control. The inherent phosphate contained in sorghum straw, and the enhanced iron (Fe) reduction and dissolution of Calcium (Ca)-bound P induced by straw addition contributed to mobilization of P in the straw incorporation treatment. In contrast, the increased poorly crystalline Al/Fe oxides-bound P and occluded Fe-bound P fraction in the combined periodic flooding-drying with straw incorporation treatment explains the decrease in CaCl2–P. Furthermore, the increased soil P sorption capacity and the decreased P desorption rate were also responsible for the reduced P loss risk in the treatment. The results of structural equation modelling (SEM) indicated that organically complexed Fe and Fe-bound P were directly affecting P mobilization in the amended soil. Overall, the present study shows that appropriate flooding-drying events coupled with straw incorporation could be a mitigation practice for stabilizing P in red mud-amended soil. However, before it can be applied on a wide scale, multi-point and field trials should be carried out to further evaluate actual environmental implications.

Formation of oriented layered MoS2 from amorphous thin film revealed by polarized x-ray absorption spectroscopy

MoS2 is a prototypical two-dimensional van der Waals (vdW) solid, where covalently bonded S–Mo–S triplets are held together by weaker vdW forces. In this work, we have studied structural transformation from a three-dimensional amorphous phase of MoS2 into a layered vdW crystal using S L2,3 edge x-ray absorption near-edge structure (XANES) spectroscopy with in-plane and out-of-plane polarized x-ray beam. The crystallization process, which starts from an isotropic amorphous phase, is accompanied by the establishment of vdW interaction between covalently bonded layers, resulting in the anisotropic nature of the crystalline phase. We have disclosed that the preferential growth of MoS2 layers along the (200) Bragg reflection commences immediately from the amorphous phase with no intermediate crystal orientations. We have additionally identified a unique signature in the S L2,3 edge spectrum that is associated with vdW bonds and can be possibly used to determine sulfur-based single-layered and multi-layered transition metal dichalcogenides.

Temperature Dependence of Yb Valence in an Au–Al–Yb Intermediate-Valence Quasicrystal Investigated by Yb <i>L</i><sub>3</sub>-Edge X-ray Absorption Near-Edge Structure Spectroscopy

In this paper, we investigate the temperature dependence of Yb valence in an Au–Al–Yb intermediate-valence quasicrystal by Yb L3-edge synchrotron X-ray absorption near-edge structure spectroscopy. The Yb valence of 2.61+ at room temperature decreases monotonically as the temperature decreases, indicating that the Yb ionic radius increases as the temperature decreases and is consistent with the anomalous suppression of the thermal shrinkage of this quasicrystal by cooling, as previously reported. The Yb valence changes by −0.053 on cooling from 298 to 2 K, and its change is more gradual on the high-temperature side than on the low-temperature side with the boundary around 200 K. Additionally, the effect of the changes in the Yb valence on the volume is quantitatively examined. The ratio of the volume changes due to the change in Yb valence per Yb atom, ΔVYb, to the amount of change in Yb valence, Δν, which is expressed as ΔVYb/Δν, was evaluated. The value of ΔVYb/Δν was estimated to be −2.8 Å3/unit Yb valence/Yb atom, whose value was close to that evaluated for YbInCu4.

Enhanced phosphorus mobility in a calcareous soil with organic amendments additions: Insights from a long term study with equal phosphorus input

The agricultural practice of replacing chemical fertilizers with organic amendments (manure and/or straw) may have consequences for phosphorus (P) loss to the environment. Such a knowledge gap was examined using a ten-year field trial in calcareous soil containing four treatments with the equal annual P input but varied organic amendment combinations as follows: mineral fertilizer only as control (MF), mineral fertilizer coupled with manure (MM), mineral fertilizer coupled with manure and straw (MMS) and mineral fertilizer coupled with straw (MS). The soil P distribution, P fractions and speciation, Fe(III) reduction and P sorption kinetics were investigated using the chemical extraction, K edge X-ray absorption near-edge structure and Langmuir equations. The electronic shuttle capacity of soils and speciation of soil dissolved organic matter (DOM) were also evaluated using electrochemical methods, three-dimensional excitation-emission matrix fluorescence spectroscopy and Fourier transform infrared spectra methods. Results showed that soil Olsen-P and total P increased at depths of 20–40 cm in MM, MMS and MS treatments, suggesting that manure and/or straw addition significantly mobilized P in the soil profile. Manure and/or straw addition also decreased soil maximum P sorption capacity (Smax) and increased the desorption rate at depths of 0–20 cm in soil across treatments. At a depth of 0–20 cm in soil of the MS treatment, the enhanced Fe(Ⅲ) reduction coupled with a decrease of Fe-bound P supports that Fe reduction dominates the mobilization of P. The transformation of Ca bound-P to Al/Fe bound-P in a depth of 0–20 cm in soil of the MM treatment may be due to the high proportion of humic-like substances in the DOM at a depth of 0–20 cm in soil of the MM treatment, which may have caused a slight/microsite acidification. These results can help to develop optimized fertilization practices to effectively mitigate P loss from calcareous soils with manure and/or straw addition.

A Novel Approach for the Quantification of Different Inorganic and Organic Phosphorus Compounds in Environmental Samples by P L2,3-Edge X-ray Absorption Near-Edge Structure (XANES) Spectroscopy.

Phosphorus (P) is an essential element for life on Earth, with an important and oftentimes unaccounted organic biogeochemical component. Current methods for the quantification of different organic P compounds in environmental samples (e.g., soils, sediments) are based on extraction techniques and often associated with incomplete P recovery or sample changes. In this study, we present a protocol for the quantification of different organic and inorganic P species in soils using synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the P L2,3-edge. Its accuracy and precision was evaluated by analyzing 40 standard mixtures composed of seven different inorganic and organic P compounds (with a mean of R2 = 0.85). In addition, we quantified the P species of two soils and two agro-industrial byproducts using P L2,3-edge XANES spectroscopy and the results were compared with those obtained by P K-edge XANES or 31P NMR spectroscopy. Using the P L2,3-edge, we identified different organic Pspecies, including those not identified by the common P K-edge XANES. However, there is a consistent underestimation of organic polyphosphates. Overall, the application of P L2,3-edge XANES provides a higher level of information than by P K-edge XANES, although the ubiquitous use of this novel methodology is still limited to samples with a phosphorus content above 3 mg g-1.

Ab Initio Analysis of Metal-Ligand Bonding in An(COT)2 with An=Th, U in Their Ground- and Core-Excited States.

Relativistic multireference ab initio wave function calculations with the restricted active space second-order perturbation theory (RASPT2) were performed on thorocene and uranocene to determine the actinide N4,5 -edge and carbon K-edge X-ray absorption near-edge structure (XANES) intensities and the metal-ligand orbital mixing in the ground state and core-excited states. Calculated spectral intensities show very good agreement with the experiments and therefore allow detailed and unambiguous assignment of the observed spectral features. φ-type covalent bonding or antibonding interactions are observed for thorocene in the core-excited states, though not in the ground state. This is because the molecular orbital of φ symmetry, which is the in-phase combination of the ligand Lφ and the Th 5fφ orbitals, can be populated with electrons in core-excited states, whereas it is essentially unoccupied in the ground state. For uranocene, the XANES spectra do not reveal much information beyond multiplet broadening, despite the presence of distinct peaks in the spectra. Every core-excited peak is best characterized by its own set of bond orbitals, as the excited state covalency is clearly different from the ground state covalency.

First-principles calculations of the atomic structure and electronic states of LixFeF3

We calculate the atomic and electronic structures of trirutile-type ${\mathrm{Li}}_{x}{\mathrm{FeF}}_{3}\phantom{\rule{4pt}{0ex}}(x=0,0.25,0.5,0.75,\phantom{\rule{4pt}{0ex}}\text{and}\phantom{\rule{4pt}{0ex}}1)$ by first-principles calculations and evaluate the relative stability among the optimized structures by energy analysis. ${\mathrm{Li}}_{0.5}{\mathrm{FeF}}_{3}$ is more stable than the three-phase coexistence of ${\mathrm{FeF}}_{3},{\mathrm{FeF}}_{2}$, and LiF, whereas the other compositions are unstable. The analyses of the local electron density, local atomic volume, and local atomic configurations show that the formal valence of Fe atoms decreases from trivalent (3+) to divalent (2+) after Li insertion. In addition, we calculate Fe $K$-edge x-ray absorption near-edge structure (XANES) spectra in ${\mathrm{Li}}_{x}{\mathrm{FeF}}_{3}$ and compare them with observed spectra. The calculated XANES spectra agree well with the corresponding observed spectra in areas such as the spectral shape and relative position of the main peaks associated with ${\mathrm{Fe}}^{3+}$ and ${\mathrm{Fe}}^{2+}$. In particular, partial XANES spectra of ${\mathrm{Fe}}^{3+}$ in ${\mathrm{Li}}_{x}{\mathrm{FeF}}_{3}$, for $x=0.25,0.5$, and 0.75, have a specific peak between the main peaks, associated with ${\mathrm{Fe}}^{3+}$ and ${\mathrm{Fe}}^{2+}$. The detailed study reveals that the energy level and intensity ratio of the ${\mathrm{Fe}}^{3+}$ main peaks depend on the adjacent cation site of Fe.

Mechanisms Responsible for Soil Phosphorus Availability Differences between Sprinkler and Furrow Irrigation.

From a historical perspective, human-induced soil erosion and resulting soil phosphorus (P) losses have likely occurred for thousands of years. In modern times, erosion risk and off-site P transport can be decreased if producers convert from furrow to sprinkler irrigation, but conversion may alter nutrient dynamics. Our study goal was to determine soil P dynamics in furrow- (in place since the early 1900s) versus sprinkler-irrigated (installed within the last decade) soils from four paired producer fields in Idaho. Furrow- and sprinkler-irrigated soils (0-5 cm; Aridisols) contained on average 38 and 20 mg kg of Olsen-extractable P (i.e., plant-available P), respectively; extractable P values over 40 mg kg limit Idaho producers to P application based on crop uptake only. Soil samples were also analyzed using a modified Hedley extraction. Furrow-irrigated soils contained greater inorganic P concentrations in the soluble+aluminum (Al)-bound+iron (Fe)-bound, occluded, and amorphous Fe-bound pools. Phosphorus -edge X-ray absorption near-edge structure (XANES) spectroscopy was unable to detect Fe-associated P but indicated greater amounts of apatite-like or octacalcium phosphate-like P in furrow-irrigated producer soils, while sprinkler-irrigated fields had lower amounts of apatite-like P and greater proportions of P bound to calcite. Findings from a controlled USDA-ARS sprinkler- versus furrow-irrigation study suggested that changes in P dynamics occur slowly over time, as few differences were observed. Overall findings suggest that Fe redox chemistry or changes in calcium (Ca)-associated P in flooded conditions altered P availability under furrow irrigation, even in aridic, calcareous soils, contributing to greater Olsen-extractable P concentrations in long-term furrow-irrigated fields.

Ce Substitution and Reduction Annealing Effects on Electronic States in Pr2−xCexCuO4 Studied by Cu K-edge X-ray Absorption Spectroscopy

We investigated Ce-substitution and reduction annealing effects on the electronic states at copper sites by Cu ${K}$-edge x-ray absorption near-edge structure measurements in Pr$_{2-x}$Ce$_x$CuO$_{4+\alpha-\delta}$ (PCCO) with varying $x$ and $\delta$ (the amount of oxygen loss during annealing) values. Absorption near-edge spectra were modified by Ce-substitution and reduction annealing in a similar manner with increasing $x$ and $\delta$. Considering electron doping by Ce-substitution, this similarity indicates an increase of electron number at the copper sites due to annealing $n_{\rm AN}$. Thus, the total number of electrons is determined by the amount of Ce and oxygen ions. Furthermore, quantitative analyses of the spectra clarified that the number of Cu$^+$ sites, corresponding to the induced electron number by Ce-substitution $n_{\rm Ce}$ increases linearly with $x$ in the as-sintered PCCO ($\delta=0$), whereas $n_{\rm AN}$ is not exactly equal to twice of $\delta$, which is expected from charge neutrality. For each $x$-fixed sample, $n_{\rm AN}$ tends to exceed 2$\delta$ with increasing $\delta$, suggesting the emergence of two types of carrier due to annealing.

Investigating nanoscale mineral compositions: IronL3-edge spectroscopic evaluation of iron oxide and oxy-hydroxide coordination

The iron (Fe) L 2,3 -edge X-ray absorption near-edge structure (XANES) spectrum is sensitive to the local coordination environment around the Fe metal center, making it a useful probe for understanding Fe mineral speciation. The two dominant spectral peaks in the Fe L 3 -edge are parameterized according to the difference in the energy position (ΔeV), and the quotient (intensity ratio) of the two peaks’ maxima. Variations in the ΔeV value are strongly linked to factors that impact on the strength of the ligand field (e.g., Fe valence state, coordination number, and the nature of ligand bonding). The intensity ratio is affected by the strength of the ligand field and by the composition of the resultant molecular orbitals. The Fe valence state also strongly affects the intensity ratio, and an intensity ratio equal to one can be used to distinguish between Fe 2+ and Fe 3+ minerals. The effects of polyhedral distortion on the magnitudes of ΔeV and intensity ratio values were tested by considering the Fe oxide and -oxy-hydroxide mineral system, in which ligand effects are limited to the differences between the oxygen and hydroxyl ligands. In this system, the distribution of Fe oxide and -oxy-hydroxide minerals on a ΔeV vs. intensity ratio two-parameter plot could be explained by considering the Fe valence state, the ligand chemistry and the site symmetry of the Fe polyhedra. Furthermore, the ΔeV and intensity ratio values were found to be anti-correlated with respect to the various distortion measures considered in this study (e.g., polyhedral volume distortion percentage). This two-parameter plot is thus presented as a standard-less phase-specific identification tool for use in Fe speciation studies, applicable to both natural systems (e.g., aerosols, aquatic colloids) as well as to engineered systems (e.g., nanoparticle synthesis). A major advantage of this technique is that it is applicable to both crystalline and poorly crystalline phases, thus enhancing our ability to study amorphous and nano-crystalline phases that are typically difficult to characterize using X-ray diffraction techniques.

Evolution of Eu valence and superconductivity in layered Eu0.5La0.5FBiS2−xSex system

We have studied the effect of Se substitution on Eu valence in a layered ${\mathrm{Eu}}_{0.5}{\mathrm{La}}_{0.5}{\mathrm{FBiS}}_{2\ensuremath{-}x}{\mathrm{Se}}_{x}$ superconductor using a combined analysis of x-ray absorption near-edge structure (XANES) and x-ray photoelectron spectroscopy (XPS) measurements. Eu ${L}_{3}$-edge XANES spectra reveal that Eu is in the mixed valence state with coexisting ${\mathrm{Eu}}^{2+}$ and ${\mathrm{Eu}}^{3+}$. The average Eu valence decreases sharply from $\ensuremath{\sim}2.3$ for $x=0.0$ to $\ensuremath{\sim}2.1$ for $x=0.4$. Consistently, Eu $3d$ XPS shows a clear decrease in the average valence by Se substitution. Bi $4f$ XPS indicates that effective charge carriers in the ${\mathrm{BiCh}}_{2}$ (Ch = S, Se) layers are slightly increased by Se substitution. On the basis of the present results it has been discussed that the metallic character induced by Se substitution in ${\mathrm{Eu}}_{0.5}{\mathrm{La}}_{0.5}{\mathrm{FBiS}}_{2\ensuremath{-}x}{\mathrm{Se}}_{x}$ is likely to be due to increased in-plane orbital overlap driven by reduced in-plane disorder that affects the carrier mobility.

Analysis of the atomic structure of colloidal quantum dots of the CdSe family: X-ray spectral diagnostics and computer modelling

Colloidal quantum dots of the CdSe family have been studied by X-ray absorption near edge structure (XANES) spectroscopy and computer modelling. CdK edge XANES spectra in colloidal quantum dots based on varisized CdSe nanoparticles have been recorded. Atomic structure of CdSe particles and also CdSe particles doped by transition metal atoms Mn and Co has been modelled based on the density functional theory. The embedding of the doping atoms is shown to result in considerable changes in the local atomic structure of CdSe particles. XANES spectra have been calculated above the CdK edge in CdSe particles, above the MnK edge in CdSe:Mn particles, above the CoK edge in CdSe:Co particles. The sensitivity of XANES spectroscopy to small changes in structural parameters of the nanoparticles of CdSe family has been demonstrated that furnishes an opportunity to apply it for the verification of atomic structure parameters around positions of cadmium and doping atoms of transition metals in quantum dots based on CdSe.

Structure and Bonding in Amorphous Cr1–xCx Nanocomposite Thin Films: X-ray Absorption Spectra and First-Principles Calculations

The local structure and chemical bonding in two-phase amorphous Cr$_{1-x}$C$_{x}$ nanocomposite thin films are investigated by Cr $K$-edge ($1s$) X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies in comparison to theory. By utilizing the computationally efficient \textit{stochastic quenching} (SQ) technique, we reveal the complexity of different Cr-sites in the transition metal carbides, highlighting the need for large scale averaging to obtain theoretical XANES and EXAFS spectra for comparison with measurements. As shown in this work, it is advantageous to use \textit{ab initio} theory as an assessment to correctly model and fit experimental spectra and investigate the trends of bond lengths and coordination numbers in complex amorphous materials. With sufficient total carbon content ($\geq$ 30 at\%), we find that the short-range coordination in the amorphous carbide phase exhibit similarities to that of a Cr$_{7}$C$_{3\pm{}y}$ structure, while excessive carbons assemble in the amorphous carbon phase.

Determination of the local structure of CsBi4-xPbxTe6 (x = 0, 0.5) by X-ray absorption spectroscopy.

We have studied the local structure and valence electronic unoccupied states of thermoelectric CsBi4Te6 and superconducting CsBi3.5Pb0.5Te6 (Tc ∼ 3 K) by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) measurements. The Bi-L3 edge EXAFS reveals wide Bi-Te distance distribution for both compounds indicating complex atomic arrangements in the studied system. The mean square relative displacements (MSRDs) of the Bi-Te bond distances appear largely increased in Pb substituted system due to larger overall local disorder, however, one of the Bi-Te bonds shows a reduced disorder. On the other hand, the Bi-L3 edge XANES is hardly affected by Pb substitution while the Te-L1 edge XANES reveals increased density of unoccupied Te 5p states. This suggests that the carriers introduced by the Pb substitution in CsBi4-xPbxTe6 preferentially goes on Te sites. Similarly, the Cs-L3 edge XANES also shows small changes due to Pb-substitution and reduced local disorder indicated by the reduced width of the Cs-L3 edge white line. We have also shown that the X-ray photoemission spectroscopy (XPS) measurements on various electronic core levels are in a qualitative agreement with the XANES results. These findings are consistent with carrier doping and a reduced disorder in one direction to be likely factors to drive the thermoelectric CsBi4Te6 into a bulk superconductor by Pb-substitution in CsBi4-xPbxTe6.

Anomalous structural behavior in the metamagnetic transition of FeRh thin films from a local viewpoint

The metamagnetic transition in FeRh thin films has been investigated via temperature-dependent x-ray-absorption fine-structure spectroscopy in order to gain correlations between magnetization and local electronic and geometric structures. According to the Fe and Rh $K$-edge x-ray-absorption near-edge structure (XANES), strong hybridization between Fe and Rh was revealed to exist. This Fe-Rh hybridization was observed to decrease during the phase transition from the antiferromagnetic (AFM) to ferromagnetic (FM) phases from the systematic change in the Fe $K$-edge XANES. In addition, only the Debye-Waller factor of the Fe-Fe pair in the AFM phase was observed to be considerably enhanced when compared with that in the FM phase, which was ascribed to local structural fluctuation inherent in the AFM phase. By considering the different features of the exchange interactions in Fe-Rh and Fe-Fe, this anomalous behavior is interpreted as being consistent with the recent theoretical study proposing the local fluctuations of spin and structure. Therefore, we consider that the local spin and Fe-Fe distance fluctuations play an important role in driving the metamagnetic transition, whereas the Fe-Rh hybridization correlates with the static stability of each magnetic phase.