Kβ Emission Spectra Research Articles

Sulfur Speciation in Li-S Batteries Determined by Operando Laboratory X-ray Emission Spectroscopy.

In this work, operando sulfur X-ray emission measurements on a Li-S battery cathode were performed using a laboratory setup as an alternative to more common synchrotron radiation based absorption studies. Photoexcitation by an X-ray tube was used. Valence-to-core Kβ X-ray emission spectra were recorded with a wavelength dispersive crystal spectrometer in von Hamos geometry, providing excellent energy resolution and good detection efficiency. The setup was used to record ex situ S Kβ emission spectra from S cathodes from the Li-S battery and also under operando conditions. Average S oxidation state within the battery cathode during battery cycling was determined from the shape of the Kβ emission spectra. A more detailed S species characterization was performed by fitting a linear combination of previously measured laboratory synthesized standards to the measured spectra. Relative amounts of different S species in the cathode were determined during the cycling of the Li-S battery. The main advantage of X-ray emission spectroscopy is that it can be performed on concentrated samples with S loading comparable to a real battery. The approach shows great promise for routine laboratory analysis of electrochemical processes in Li-S batteries and other sulfur-based systems under operando conditions.

In-air micro-PIXE chemical state analysis of phosphorus and sulfur using a new parallel-beam wavelength-dispersive X-ray emission spectrometer

The proton induced K X-ray emission spectra of several different phosphorus and sulfur compounds were recorded with the new parallel-beam wavelength dispersive X-ray emission spectrometer. The spectrometer was installed recently at the external proton microbeam at the J. Stefan Institute to perform high energy resolution in-air micro-PIXE analysis in the tender X-ray range. Reported measurements are used to probe the capabilities of the spectrometer to perform also chemical state analysis. For phosphorus measurements, where the energy resolution of the spectrometer is the highest, a clear correlation between measured energy position of the Kα emission line and the phosphorus formal oxidation state is obtained. Chemical contrast is increased further in the Kβ emission spectra reflecting the structure of occupied valence molecular orbitals defined by the first coordination shell around the central phosphorus atom. A reasonable chemical contrast is maintained also in the sulfur Kβ emission spectra, despite the fact that the energy resolution of the spectrometer declines with increasing X-ray energy. Finally, an example of phosphorus speciation in reference biological material is presented, demonstrating the feasibility of the new setup to extend the capabilities of in-air micro-PIXE analysis towards chemical speciation.

Pressure-induced transitions in RCo5 (R = Y, La) studied by x-ray emission spectroscopy, x-ray diffraction and density functional theory

The hydrostatic pressure dependent evolution of the electronic and magnetic structure of LaCo5 and YCo5 was investigated by means of x-ray emission spectroscopy, x-ray diffraction, and spin-polarized density functional theory (DFT) calculations. Using experimental lattice parameters the DFT correctly predicts the pressure of the magnetic transition in both compounds to be 26 GPa (La) and 22–23 GPa (Y). The transition was experimentally resolved in the changes of the electronic structure via the integrated absolute difference of the Co Kβ emission spectra. Comparison of theory and experiment confirm for the first time a common feature in both LaCo5 and YCo5 to be the source of the transition; the Fermi-level crossing of an up-spin polarized flat band driving the systems into a low spin configuration via a Lifshitz type transition of the Fermi surface. Another phase transition observed around 12 GPa in LaCo5 was clarified to be caused by the change in the down-spin density of states at the Fermi level.

Resonant X-ray Emission Spectroscopy with a SASE Beam

Aqueous iron (III) oxide nanoparticles were irradiated with pure self-amplified spontaneous emission (SASE) X-ray free-electron laser (XFEL) pulses tuned to the energy around the Fe K-edge ionization threshold. For each XFEL shot, the incident X-ray pulse spectrum and Fe Kβ emission spectrum were measured synchronously with dedicated spectrometers and processed through a reconstruction algorithm allowing for the determination of Fe Kβ resonant X-ray emission spectroscopy (RXES) plane with high energy resolution. The influence of the number of X-ray shots employed in the experiment on the reconstructed data quality was evaluated, enabling the determination of thresholds for good data acquisition and experimental times essential for practical usage of scarce XFEL beam times.

Characterization of Li-S Batteries Using Laboratory Sulfur X-ray Emission Spectroscopy.

Application of laboratory-based X-ray analytical techniques that are capable of a reliable characterization of the chemical state of sulfur within bulk battery cathode in parallel with electrochemical characterization is essential for further development of lithium–sulfur batteries. In this work, MeV proton-induced X-ray emission (XES) sulfur measurements were performed in ex situ mode on laboratory-synthesized sulfur standards and precycled battery cathodes. The average sulfur charge was determined from the energy shift of the Kα emission line and from the spectral shape of the Kβ emission spectrum. Finally, operando Kα XES measurements were performed to monitor reduction of sulfur within battery cathode during discharge. The experimental approach presented here provides an important step toward more routine laboratory analysis of sulfur-based battery systems and also other sulfur-neighboring low-Z bulk materials with emission energies in the tender X-ray range.

Chemical effects in K emission spectra of 38Sr compounds

The recent advances in the instrumental operating detection system provide better understanding of the several atomic parameters such as characteristic x-ray emission lines, relative intensity ratio and line-width, transition probabilities, Coster-Kronig transitions and fluorescence yields. At present, the qualitative and quantitative analysis in wavelength dispersive spectrometers are routinely performed by the fundamental parameter approach method, but none of the approach has been implemented in the routine analysis to test the possible influence of chemical effects in the different compounds. The study of chemical effects with high resolution curved crystals offers a great opportunity to enhance the analytical potential of WDXRF instruments. In the present work, high resolution Kα and Kβ emission spectra of 38Sr compounds has been measured with wavelength dispersive spectrometer. First time, spectral structures correlated to the satellite lines and their energy differences are determined. In Kα energy region, two satellite peaks (Kα3 and Kα4) are observed. The possible causes of energy shifts such as effective charge, relative intensity ratio and line-width, screening effect, shake process and electro-negativity and their roles in different 38Sr compounds are also discussed.

Relation between the Co-O bond lengths and the spin state of Co in layered Cobaltates: a high-pressure study

The pressure-response of the Co-O bond lengths and the spin state of Co ions in a hybrid 3d-5d solid-state oxide Sr2Co0.5Ir0.5O4 with a layered K2NiF4-type structure was studied by using hard X-ray absorption and emission spectroscopies. The Co-K and the Ir-L3 X-ray absorption spectra demonstrate that the Ir5+ and the Co3+ valence states at ambient conditions are not affected by pressure. The Co Kβ emission spectra, on the other hand, revealed a gradual spin state transition of Co3+ ions from a high-spin (S = 2) state at ambient pressure to a complete low-spin state (S = 0) at 40 GPa without crossing the intermediate spin state (S = 1). This can be well understood from our calculated phase diagram in which we consider the energies of the low spin, intermediate spin and high spin states of Co3+ ions as a function of the anisotropic distortion of the octahedral local coordination in the layered oxide. We infer that a short in-plane Co-O bond length (<1.90 Å) as well as a very large ratio of Co-Oapex/Co-Oin-plane is needed to stabilize the IS Co3+, a situation which is rarely met in reality.

Investigation of K X-ray intensity ratios of some 4d transition metals depending on the temperature

In this paper, we have studied the intensity ratios Kβ/Kα depending on the temperature for transition elements Mo, Nb, Zr and Y by 59.5keV γ-rays from a 100 mCi 241Am radioisotope point source. The Kα and Kβ emission spectra of Mo, Nb, Zr and Y were measured by using a Si (Li) solid-state detector at temperature between 40 and 400°C. σKα and σKβ production cross-sections, Kβ/Kα intensity ratios, asymmetry factor, energy shifts and full width half maximum (FWHM) values of the elements have been calculated. Temperature-dependent changes of the parameters are tabulated and given in the graphical forms. Based on the results obtained, Kβ/Kα X-ray intensity ratios of the elements are dependent on the temperature. It is shown that σKβ fluorescence cross sections of Mo, Nb and Zr have more increase rate than σKα fluorescence cross sections with increasing temperature. For Y, σKα and σKβ production cross-sections firstly decrease, then increase. In general, Kβ/Kα X-ray intensity ratios tend to increase with increasing temperature. Some significant shifts are observed in Kα and Kβ emission spectra of Mo and Y. These results may contribute to the XRF studies of transition metals.

Experimental and theoretical correlations between vanadium K-edge X-ray absorption and Kβ emission spectra.

A series of vanadium compounds was studied by K-edge X-ray absorption (XAS) and Kbeta X-ray emission spectroscopies (XES). Qualitative trends within the datasets, as well as comparisons between the XAS and XES data, illustrate the information content of both methods. The complementary nature of the chemical insight highlights the success of this dual-technique approach in characterizing both the structural and electronic properties of vanadium sites. In particular, and in contrast to XAS or extended X-ray absorption fine structure (EXAFS), we demonstrate that valence-to-core XES is capable of differentiating between ligating atoms with the same identity but different bonding character. Finally, density functional theory (DFT) and time-dependent DFT calculations enable a more detailed, quantitative interpretation of the data. We also establish correction factors for the computational protocols through calibration to experiment. These hard X-ray methods can probe vanadium ions in any oxidation or spin state, and can readily be applied to sample environments ranging from solid-phase catalysts to biological samples in frozen solution. Thus, the combined XAS and XES approach, coupled with DFT calculations, provides a robust tool for the study of vanadium atoms in bioinorganic chemistry.Electronic supplementary materialThe online version of this article (doi:10.1007/s00775-016-1358-7) contains supplementary material, which is available to authorized users.

Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid.

In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range.

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News Article

Chemical State Analysis of Phosphorus Performed by X-ray Emission Spectroscopy

An experimental and theoretical study of phosphorus electronic structure based on high energy resolution X-ray emission spectroscopy was performed. The Kα and Kβ emission spectra of several phosphorus compounds were recorded using monochromatic synchrotron radiation and megaelectronvolt (MeV) proton beam for target excitation. Measured spectra are compared to the results of ab initio quantum chemical calculations based on density functional theory (DFT). Clear correlation between energy position of the Kα emission line and the phosphorus formal oxidation state as well as DFT-calculated number of valence electrons is obtained; measured energy shifts are reproduced by the calculations. Chemical sensitivity is increased further by looking at the Kβ emission spectra probing directly the structure of occupied molecular orbitals. Energies and relative intensities of main components are given together with the calculated average atomic character of the corresponding molecular orbitals involved in transitions.

A study of K shell X-ray intensity ratios of NixCr1−x alloys in external magnetic field and determination of effective atomic numbers of these alloys

In this study, the effect of external magnetic field on the Kβ/Kα X-ray intensity ratios of various alloy compositions of Ni–Cr transition metal alloys has been investigated. The Kα and Kβ emission spectra of Ni, Cr and NixCr1−x (x=0.40; 0.50; 0.60; 0.80) alloys were measured by using a Si (Li) solid-state detector. Kβ/Kα X-ray intensity ratios of Ni, Cr and NixCr1−x alloys without magnetic field and in 0.5 and 1 T external magnetic field have been measured following excitation by 59.5 keV γ-rays from a 200 mCi241Am radioisotope point source. When the experimental data obtained in external magnetic field have been compared with data without external magnetic field, deviations have been observed in Kβ/Kα X-ray intensity ratios for Ni and Cr in different alloy compositions. Thus, results of these measurements have shown that Kβ/Kα X-ray intensity ratios of Ni and Cr in NixCr1−x alloys are dependent on the external magnetic field. Also the total mass attenuation coefficients for pure 3d transition metals and their alloys at different compositions were measured and theoretically estimated using mixture rule for selected photon energy. Later on, total atomic and electronic cross-sections and effective atomic number for alloys are determined experimentally and theoretically using these mass attenuation coefficients. When these parameters are examined depending on the alloy compositions, thereof have been found to vary with the alloy composition.

A Complete High-to-Low spin state Transition of Trivalent Cobalt Ion in Octahedral Symmetry in SrCo0.5Ru0.5O3-δ

The complex metal oxide SrCo0.5Ru0.5O(3-δ) possesses a slightly distorted perovskite crystal structure. Its insulating nature infers a well-defined charge distribution, and the six-fold coordinated transition metals have the oxidation states +5 for ruthenium and +3 for cobalt as observed by X-ray spectroscopy. We have discovered that Co(3+) ion is purely high-spin at room temperature, which is unique for a Co(3+) in an octahedral oxygen surrounding. We attribute this to the crystal field interaction being weaker than the Hund's-rule exchange due to a relatively large mean Co-O distances of 1.98(2) Å, as obtained by EXAFS and X-ray diffraction experiments. A gradual high-to-low spin state transition is completed by applying high hydrostatic pressure of up to 40 GPa. Across this spin state transition, the Co Kβ emission spectra can be fully explained by a weighted sum of the high-spin and low-spin spectra. Thereby is the much debated intermediate spin state of Co(3+) absent in this material. These results allow us to draw an energy diagram depicting relative stabilities of the high-, intermediate-, and low-spin states as functions of the metal-oxygen bond length for a Co(3+) ion in an octahedral coordination.

Bridging-hydride influence on the electronic structure of an [FeFe] hydrogenase active-site model complex revealed by XAES-DFT

Two crystallized [FeFe] hydrogenase model complexes, 1 = (μ-pdt)[Fe(CO)(2)(PMe(3))](2) (pdt = SC1H2C2H2C3H2S), and their bridging-hydride (Hy) derivative, [1Hy](+) = [(μ-H)(μ-pdt)[Fe(CO)(2) (PMe(3))](2)](+) (BF(4)(−)), were studied by Fe K-edge X-ray absorption and emission spectroscopy, supported by density functional theory. Structural changes in [1Hy](+) compared to 1 involved small bond elongations (<0.03 Å) and more octahedral Fe geometries; the Fe–H bond at Fe1 (closer to pdt-C2) was ~0.03 Å longer than that at Fe2. Analyses of (1) pre-edge absorption spectra (core-to-valence transitions), (2) Kβ(1,3), Kβ', and Kβ(2,5) emission spectra (valence-to-core transitions), and (3) resonant inelastic X-ray scattering data (valence-to-valence transitions) for resonant and non-resonant excitation and respective spectral simulations indicated the following: (1) the mean Fe oxidation state was similar in both complexes, due to electron density transfer from the ligands to Hy in [1Hy](+). Fe 1s→3d transitions remained at similar energies whereas delocalization of carbonyl AOs onto Fe and significant Hy-contributions to MOs caused an ~0.7 eV up-shift of Fe1s→(CO)s,p transitions in [1Hy](+). Fed-levels were delocalized over Fe1 and Fe2 and degeneracies biased to O(h)–Fe1 and C(4v)–Fe2 states for 1, but to O(h)–Fe1,2 states for [1Hy](+). (2) Electron-pairing of formal Fe(d(7)) ions in low-spin states in both complexes and a higher effective spin count for [1Hy](+) were suggested by comparison with iron reference compounds. Electronic decays from Fe d and ligand s,p MOs and spectral contributions from Hys,p→1s transitions even revealed limited site-selectivity for detection of Fe1 or Fe2 in [1Hy](+). The HOMO/LUMO energy gap for 1 was estimated as 3.0 ± 0.5 eV. (3) For [1Hy](+) compared to 1, increased Fed (x(2) − y(2)) − (z(2)) energy differences (~0.5 eV to ~0.9 eV) and Fed→d transition energies (~2.9 eV to ~3.7 eV) were assigned. These results reveal the specific impact of Hy-binding on the electronic structure of diiron compounds and provide guidelines for a directed search of hydride species in hydrogenases.

Site-Selective X-ray Spectroscopy on an Asymmetric Model Complex of the [FeFe] Hydrogenase Active Site

The active site for hydrogen production in [FeFe] hydrogenase comprises a diiron unit. Bioinorganic chemistry has modeled important features of this center, aiming at mechanistic understanding and the development of novel catalysts. However, new assays are required for analyzing the effects of ligand variations at the metal ions. By high-resolution X-ray absorption spectroscopy with narrow-band X-ray emission detection (XAS/XES = XAES) and density functional theory (DFT), we studied an asymmetrically coordinated [FeFe] model complex, [(CO)(3)Fe(I)1-(bdtCl(2))-Fe(I)2(CO)(Ph(2)P-CH(2)-NCH(3)-CH(2)-PPh(2))] (1, bdt = benzene-1,2-dithiolate), in comparison to iron-carbonyl references. Kβ emission spectra (Kβ(1,3), Kβ') revealed the absence of unpaired spins and the low-spin character for both Fe ions in 1. In a series of low-spin iron compounds, the Kβ(1,3) energy did not reflect the formal iron oxidation state, but it decreases with increasing ligand field strength due to shorter iron-ligand bonds, following the spectrochemical series. The intensity of the valence-to-core transitions (Kβ(2,5)) decreases for increasing Fe-ligand bond length, certain emission peaks allow counting of Fe-CO bonds, and even molecular orbitals (MOs) located on the metal-bridging bdt group of 1 contribute to the spectra. As deduced from 3d → 1s emission and 1s → 3d absorption spectra and supported by DFT, the HOMO-LUMO gap of 1 is about 2.8 eV. Kβ-detected XANES spectra in agreement with DFT revealed considerable electronic asymmetry in 1; the energies and occupancies of Fe-d dominated MOs resemble a square-pyramidal Fe(0) for Fe1 and an octahedral Fe(II) for Fe2. EXAFS spectra for various Kβ emission energies showed considerable site-selectivity; approximate structural parameters similar to the crystal structure could be determined for the two individual iron atoms of 1 in powder samples. These results suggest that metal site- and spin-selective XAES on [FeFe] hydrogenase protein and active site models may provide a powerful tool to study intermediates under reaction conditions.

Study of N-bridged diiron phthalocyanine relevant to methane oxidation: Insight into oxidation and spin states from high resolution 1s core hole X-ray spectroscopy

μ-Nitrido diiron phthalocyanine [PcFe+3.5NFe+3.5Pc]0 is a highly efficient catalyst, able to oxidize methane under near-ambient conditions. In this work, high resolution X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS) were applied to study iron species in the series of μ-nitrido diiron phthalocyanines including initial [PcFe+3.5NFe+3.5Pc]0 and oxidized complexes [PcFeIVNFeIVPc]+PF6 and [PcFeIVNFeIV(Pc+)]2+Br2 as model compounds for the intermediates in the catalytic cycle. These systems contain 3d4 configuration of iron in high oxidation state Fe(IV). XES spectra of Kβ line are sensible to the local iron spin density and show unexpected difference in the spin state between the initial [PcFe+3.5NFe+3.5Pc]0 (LS), one-electron oxidized [PcFeIVNFeIVPc]+PF6 (HS) and two electron oxidized cation radical species [PcFeIVNFeIV(Pc+)]2+Br2 (LS). Fe K-edge XANES spectra were recorded at the fluorescence energy of the main Kβ1,3 line or Kβ′ line in the Kβ emission spectrum. The conclusions of RIXS study corroborated XES data. Our study suggests that the main catalytic pathway of oxidation includes two-electron transformation from the LS initial complex to the LS two–electron oxidized [PcFeIVNFeIV(Pc+)(O)]0 to generate powerful oxidant able to oxidize methane via two-electron process.

Characterization of EUV periodic multilayers

AbstractNanometric Co/Mg, Co/Mg/B4C, Al/SiC and Al/Mo/SiC periodic multilayers deposited by magnetron sputtering are studied in order to correlate their optical performances in the extreme ultraviolet (EUV) range to their structural quality. To that purpose, our recently developed methodology based on high‐resolution X‐ray emission spectroscopy (XES) and X‐ray and EUV reflectometry is now extended to nuclear magnetic resonance (NMR) spectroscopy and time‐of‐flight secondary ions mass spectrometry (ToF‐SIMS). The analysis of the Co Lαβ and Mg Kβ emission spectra shows that the Co and Mg atoms within the multilayers are in a chemical state equivalent to that of the atoms in the pure Co and Mg references, respectively. But NMR spectra give evidence for a reaction between Co atoms and B and/or C atoms from B4C. The Al and Si Kβ emission spectra do not reveal the formation of an interfacial compound in Al/SiC and Al/Mo/SiC. Only the roughness limits the optical quality of Al/SiC. The comparative analysis of the ToF‐SIMS spectra of Al/SiC and Al/Mo/SiC indicates that the structural quality is enhanced when Mo is introduced within the stack. Copyright © 2011 John Wiley &amp; Sons, Ltd.

Speculations on anomalous chemical states of Ti ions in FeTiO3 observed by high-resolution X-ray Kβ emission spectra

A series of high-resolution Ti Kβ X-ray emission spectra were measured for various isomorphous titanium oxides with composition MTiO3, where M was divalent Mg, Mn, Fe, Co, or Ni. The detailed spectral features of Ti Kβ lines for MTiO3 were intermediate between those of TiO2 and Ti2O3 depending on the coexisting cation species M, though the formal valence states of all Ti ions in MTiO3 were consistent with those in TiO2. Especially in the case of FeTiO3, the features in both main and satellite lines had many similarities of Ti2O3. The Ti Kβ X-rays of FeTiO3 seemed to be emitted by the transition from Ti3+-like states. Because of the small difference in energies and the large overlap between Ti 3d and Fe 3d orbitals, intermediate core-hole states occurring on the X-ray emission process might produce the inter-valence charge transfer from Fe2+ to Ti4+ to form the Ti3+-like states. The DV Xα calculations based on the molecular orbital theory can reproduce the satellite structures to assume the increasing 3d electron densities on Ti for FeTiO3.

High resolution study of Kβ′ and Kβ1,3 X-ray emission lines from Mn-compounds

Abstract High-resolution Kβ emission spectra of several manganese compounds were measured in order to characterize the dependence of the Kβ′ and Kβ 1,3 features, on the chemical environment. High resolution spectra were obtained using a non-conventional spectrometer based on quasi-back-diffraction geometry at National Synchrotron Light Laboratory (LNLS). It was found that the energy of the Kβ′ satellite structure relative to the main Kβ 1,3 line decreases linearly with the formal oxidation state for Mn–O systems. A noticeable dispersion of the relative Kβ′ energy for different Mn 2+ compounds could be observed. The dependence of the Kβ′ satellite line on the net charge and the effective 3 d spin in Mn 2+ compounds was investigated. Calculations of the net charge and the effective 3 d spin were performed within the density-functional theory using the package SIESTA. A direct relation between this dispersion and the effective Mn 3 d spin was found.