X-ray Emission Spectra Research Articles

Chemistry of zipping reactions in mesoporous carbon consisting of minimally stacked graphene layers.

The structural evolution of highly mesoporous templated carbons is examined from temperatures of 1173 to 2873 K to elucidate the optimal conditions for facilitating graphene-zipping reactions whilst minimizing graphene stacking processes. Mesoporous carbons comprising a few-layer graphene wall display excellent thermal stability up to 2073 K coupled with a nanoporous structure and three-dimensional framework. Nevertheless, advanced temperature-programmed desorption (TPD), X-ray diffraction, and Raman spectroscopy show graphene-zipping reactions occur at temperatures between 1173 and 1873 K. TPD analysis estimates zipping reactions lead to a 1100 fold increase in the average graphene-domain, affording the structure a superior chemical stability, electrochemical stability, and electrical conductivity, while increasing the bulk modulus of the framework. At above 2073 K, the carbon framework shows a loss of porosity due to the development of graphene-stacking structures. Thus, a temperature range between 1873 and 2073 K is preferable to balance the developed graphene domain size and high porosity. Utilizing a neutron pair distribution function and soft X-ray emission spectra, we prove that these highly mesoporous carbons already consist of a well-developed sp2-carbon network, and the property evolution is governed by the changes in the edge sites and stacked structures.

X-ray Emission Spectroscopy of Single Protein Crystals Yields Insights into Heme Enzyme Intermediates.

Enzyme reactivity is often enhanced by changes in oxidation state, spin state, and metal-ligand covalency of associated metallocofactors. The development of spectroscopic methods for studying these processes coincidentally with structural rearrangements is essential for elucidating metalloenzyme mechanisms. Herein, we demonstrate the feasibility of collecting X-ray emission spectra of metalloenzyme crystals at a third-generation synchrotron source. In particular, we report the development of a von Hamos spectrometer for the collection of Fe Kβ emission optimized for analysis of dilute biological samples. We further showcase its application in crystals of the immunosuppressive heme-dependent enzyme indoleamine 2,3-dioxygenase. Spectra from protein crystals in different states were compared with relevant reference compounds. Complementary density functional calculations assessing covalency support our spectroscopic analysis and identify active site conformations that correlate to high- and low-spin states. These experiments validate the suitability of an X-ray emission approach for determining spin states of previously uncharacterized metalloenzyme reaction intermediates.

Non-resonant and resonant X-ray emission at high pressure using a von Hámos setup: the case of FeO

We present a setup exploiting a von Hámos spectrometer in order to study (resonant) X-ray emission of matter exposed to high pressure. The capabilities of this setup are demonstrated for the case of FeO at pressures between 13 GPa and 75 GPa. The setup provides high-quality Kβ 1,3 X-ray emission spectra at high pressures for iron spin state analysis within minutes and iron valence-to-core spectra in less than one hour. Resonant X-ray emission maps can be obtained on a timescale of one hour with 1.0 eV and in approximately 3 hours with 0.2 eV incident energy resolution. Both Kα and Kβ emission can be utilized to gain L-edge and M-edge-like information, respectively, with the option of measuring both simultaneously. The spin state results on FeO between 13 GPa and 75 GPa are in accordance with recent literature. The structural distortion is reflected in both, valence-to-core spectra and resonant X-ray emission maps, which showcase the great potential of the presented setup. The achieved data acquisition times are promising to couple pressure with temperature by laser heating.

Numerical Modeling of Energetic Electron Acceleration, Transport, and Emission in Solar Flares: Connecting Loop-top and Footpoint Hard X-Ray Sources

The acceleration and transport of energetic electrons during solar flares is one of the outstanding topics in solar physics. Recent X-ray and radio imaging and spectroscopy observations have provided diagnostics of the distribution of nonthermal electrons and suggested that, in certain flare events, electrons are primarily accelerated in the loop top and likely experience trapping and/or scattering effects. By combining the focused particle transport equation with magnetohydrodynamic (MHD) simulations of solar flares, we present a macroscopic particle model that naturally incorporates electron acceleration and transport. Our simulation results indicate that physical processes such as turbulent pitch-angle scattering can have important impacts on both electron acceleration in the loop top and transport in the flare loop, and their influences are highly energy-dependent. A spatial-dependent turbulent scattering with enhancement in the loop top can enable both efficient electron acceleration to high energies and transport of abundant electrons to the footpoints. We further generate spatially resolved synthetic hard X-ray (HXR) emission images and spectra, revealing both the loop-top and footpoint HXR sources. Similar to the observations, we show that the footpoint HXR sources are brighter and harder than the loop-top HXR source. We suggest that the macroscopic particle model provides new insights into understanding the connection between the observed loop-top and footpoint nonthermal emission sources by combining the particle model with dynamically evolving MHD simulations of solar flares.

Modeling Nonresonant X-ray Emission of Second- and Third-Period Elements without Core-Hole Reference States and Empirical Parameters.

Nonresonant X-ray emission (XE) energies and oscillator strengths are obtained using the effective potential of the generalized Kohn-Sham semi-canonical projected random phase approximation (GKS-spRPA) method. XE energies are estimated as a difference between the valence and core ionization eigenvalues, while the oscillator strengths are obtained within a frozen orbital approximation. This straightforward approach provides accurate XE energies without any need for core-hole reference states, empirical shifting parameters, or tuning of density functionals. To account for relativistic corrections to the core orbitals, we have formulated a scalar relativistic (sr) GKS-spRPA approach based on the spin-free X2C one-electron Hamiltonian. The sr-GKS-spRPA method provides highly reliable XE energies using uncontracted basis-sets on atoms where the core-hole is created prior to emission. For the largest basis-sets used in our study, using completely uncontracted polarized core-valence Dunning basis-sets, the mean absolute errors (MAEs) are within 0.7 eV compared to experimental reference values for a test-set consisting of 27 valence-to-core XE energies of molecules with second- and third-period elements. Considering a balance of accuracy and computational effort, we recommend the use of s-uncontracted def2-TZVP for second-period and all-uncontracted def2-TZVP for third-period elements. For this recommended basis-set, the MAE is 0.2 eV. The analytically continued sr-GKS-spRPA approach, with an computational cost, enables efficient computation of XE spectra of molecules such as S8 and C60 with several core-hole states.

Combined experimental and theoretical investigation of electronic properties of nitrides

A comprehensive study of the electronic structure of group-III nitrides (AlN, GaN, InN, and BN) crystallizing in the wurtzite, zinc-blende, and graphitelike hexagonal (BN) structures is presented. A large set of the x-ray emission and absorption spectra was collected at the several synchrotron radiation facilities at installations offering the highest possible energy resolution. By taking advantage of the linear polarization of the synchrotron radiation and making careful crystallographic orientation of the samples, the bonds along c axis (rr) and ‘‘in plane’’ (u) in the wurtzite structure could be separately examined. Particularly for AlN we found pronounced anisotropy of the studied bonds. The experimental spectra are compared directly with ab initio calculations of the partial density of states projected on the cation and anion atomic sites. For the GaN, AlN, and InN the agreement between structures observed in the calculated density of states (DOS) and structures observed in the experimental spectra is very good. In the case of hexagonal BN we have found an important influence of insufficient core screening in the x-ray spectra that influences the DOS distribution. The ionicity of the considered nitrides is also discussed.

Inside the core of a young massive star cluster: 3D MHD simulations

ABSTRACT Young massive star clusters inhabit regions of star formation and play an essential role in the galactic evolution. They are sources of both thermal and non-thermal radiation, and are effective cosmic ray accelerators. We present the 3D magnetohydrodynamic modelling of the plasma flows in a young compact cluster at the evolutionary stage comprising multiple interacting supersonic winds of massive OB and WR stars. The modelling allows studying the partitioning of the mechanical energy injected by the winds between the bulk motions, thermal heating, and magnetic fields. Cluster-scale magnetic fields reaching the magnitudes of ∼300 $\mu$G show the filamentary structures spreading throughout the cluster core. The filaments with the high magnetic fields are produced by the Axford–Cranfill-type effect in the downstream of the wind termination shocks, which is amplified by a compression of the fields with the hot plasma thermal pressure in the central part of the cluster core. The hot (∼a few keV) plasma is heated at the termination shocks of the stellar winds and compressed in the colliding post-shock flows. We also discuss a possible role of the thermal conduction effects on the plasma flow, and analyse temperature maps in the cluster core and the diffuse thermal X-ray emission spectra. The presence of high cluster-scale magnetic fields supports the possibility of high-energy cosmic ray acceleration in clusters at the given evolutionary stage.

A deep neural network for valence-to-core X-ray emission spectroscopy

ABSTRACT In this Article, we extend our XANESNET deep neural network (DNN) to predict the lineshape of first-row transition metal K-edge valence-to-core X-ray emission (VtC-XES) spectra. We demonstrate that – despite the strong sensitivity of VtC-XES to the electronic structure of the system under study – the DNN can reproduce the main spectral features from only the local coordination geometry of the transition metal complexes when encoded as a feature vector of weighted atom-centred symmetry functions (wACSF). We subsequently implement and evaluate three methods for assessing uncertainty in the predictions made by the VtC-DNN: deep ensembles, Monte-Carlo dropout, and bootstrap resampling. We show that bootstrap resampling provides the best performance when evaluated on ‘held-out’ testing data, and also demonstrates a strong correlation between the uncertainty it predicts and the error occurring between the target and predicted VtC-XES spectra. Finally, we demonstrate practical performance by application to unseen transition metal complexes across the entire first-row (Ti–Zn).

Time-resolved K-shell x-ray spectra of nanosecond laser-produced titanium tracer in gold plasmas

A study of a nanosecond laser irradiation on the titanium-layer-buried gold planar target is presented. The time-resolved x-ray emission spectra of titanium tracer are measured by a streaked crystal spectrometer. By comparing the simulated spectra obtained by using the FLYCHK code with the measured titanium spectra, the temporal plasma states, i.e., the electron temperatures and densities, are deduced. To evaluate the feasibility of using the method for the characterization of Au plasma states, the deduced plasma states from the measured titanium spectra are compared with the Multi-1D hydrodynamic simulations of laser-produced Au plasmas. By comparing the measured and simulated results, an overall agreement for the electron temperatures is found, whereas there are deviations in the electron densities. The experiment–theory discrepancy may suggest that the plasma state could not be well reproduced by the Multi-1D hydrodynamic simulation, in which the radial gradient is not taken into account. Further investigations on the spectral characterization and hydrodynamic simulations of the plasma states are needed. All the measured and FLYCHK simulated spectra are given in this paper as datasets. The datasets are openly available at http://www.doi.org/10.57760/sciencedb.j00113.00032.

Quantifying electron temperature distributions from time-integrated x-ray emission spectra.

K-shell x-ray emission spectroscopy is a standard tool used to diagnose the plasma conditions created in high-energy-density physics experiments. In the simplest approach, the emissivity-weighted average temperature of the plasma can be extracted by fitting an emission spectrum to a single temperature condition. It is known, however, that a range of plasma conditions can contribute to the measured spectra due to a combination of the evolution of the sample and spatial gradients. In this work, we define a parameterized model of the temperature distribution and use Markov Chain Monte Carlo sampling of the input parameters, yielding uncertainties in the fit parameters to assess the uniqueness of the inferred temperature distribution. We present the analysis of time-integrated S and Fe x-ray spectroscopic data from the Orion laser facility and demonstrate that while fitting each spectral region to a single temperature yields two different temperatures, both spectra can be fit simultaneously with a single temperature distribution. We find that fitting both spectral regions together requires a maximum temperature of 1310-70 +90 eV with significant contributions from temperatures down to 200eV.

Elemental mapping and iron oxidation state measurement of synthetic low-activity waste feeds

During the conversion of nuclear waste feed into glass, iron bearing precursors are incorporated into the melt and affect various properties of the melt such as viscosity and density. Laboratory-scale measurements to determine iron oxidation state could be used in cases where samples are subjected to ex-situ heat treatment and kinetic relationships developed. Typically, measurements of iron oxidation state have been limited to synchrotron X-ray absorption techniques, Mossbauer spectroscopy, or destructive wet chemical techniques. In this work, we present our method development which employs electron probe microanalysis (EPMA) to measure the oxidation state of iron. This method could also serve broader applications, not only in nuclear waste vitrification but also in commercial glass making, geology, and archaeology. Using EPMA, we measured the Fe L-edge X-ray emission spectra of nuclear waste feed samples prepared with a reduced iron precursor and heat treated to various temperatures in air. EPMA based measurements provide a cost-effective and rapid alternative to measure iron oxidation state. Furthermore, the method described in this paper allows for spatially resolved measurements with a minimum step size of 100 µm. We demonstrate that iron oxidation state can be calculated using EPMA, and we compare the calculated iron oxidation state to that measured by synchrotron Fe K-edge X-ray absorption measurements. This work demonstrates that, for nuclear waste feeds prepared with reduced iron, the oxidation state of the iron is influenced by the thermal history. Fast-drying the feed slurry produced more reduced iron in feed than previously observed in feeds prepared by slowly drying and crushing into a powder.

The local structure of water from combining diffraction and X-ray spectroscopy

We build a large (~3400 structures) library of X-ray absorption (XAS) and X-ray emission (XES) spectra computed at high level, which together with their associated structures form the basis for a Monte Carlo fit to the experimental oxygen‑oxygen pair-distribution, XAS and XES spectra for ambient liquid water. The procedure results in weights giving the relative importance of each structure to reproduce the experimental properties. We show that the information content in the X-ray spectroscopic data is strongly complementary to that of X-ray diffraction, and dependent on specific structures that are still consistent with the diffraction data. We fit simultaneously to the X-ray spectroscopy and diffraction experimental data and obtain weights on each structure that give a structural distribution that is consistent with the three experimental datasets. These weights are applied to structural parameters characterizing the local environment of each structure and result in the emergence of more preferred values of these parameters.

Core-hole delocalization for modeling x-ray spectroscopies: A cautionary tale.

The influence of core-hole delocalization for x-ray photoelectron, x-ray absorption, and x-ray emission spectrum calculations is investigated in detail using approaches including response theory, transition-potential methods, and ground state schemes. The question of a localized/delocalized vacancy is relevant for systems with symmetrically equivalent atoms, as well as near-degeneracies that can distribute the core orbitals over several atoms. We show that the issues relating to core-hole delocalization are present for calculations considering explicit core-hole states, e.g., when using a core-excited or core-ionized reference state or for fractional occupation numbers. As electron correlation eventually alleviates the issues, but even when using coupled-cluster single-double and perturbative triple, there is a notable discrepancy between core-ionization energies obtained with localized and delocalized core-holes (0.5eV for the carbon K-edge). Within density functional theory, the discrepancy correlates with the exchange interaction involving the core orbitals of the same spin symmetry as the delocalized core-hole. The use of a localized core-hole allows for a reasonably good inclusion of relaxation at a lower level of theory, whereas the proper symmetry solution involving a delocalized core-hole requires higher levels of theory to account for the correlation effects involved in orbital relaxation. For linear response methods, we further show that if x-ray absorption spectra are modeled by considering symmetry-unique sets of atoms, care has to be taken such that there are no delocalizations of the core orbitals, which would otherwise introduce shifts in absolute energies and relative features.

First studies of the diffuse X-ray emission in the Large Magellanic Cloud with eROSITA

Context. In the first months after its launch in July 2019, the extended Roentgen Survey with an Imaging Telescope Array (eROSITA) on board Spektrum-Roentgen-Gamma performed long-exposure observations in the regions around supernova (SN) 1987A and super-nova remnant (SNR) N132D in the Large Magellanic Cloud (LMC). Aims. We analysed the distribution and the spectrum of the diffuse X-ray emission in the observed fields to determine the physical properties of the hot phase of the interstellar medium (ISM). Methods. Spectral extraction regions were defined using the Voronoi tessellation method. The spectra were fit with a combination of thermal and non-thermal emission models. The eROSITA data are complemented by newly derived column density maps for the Milky Way and the LMC, 888 MHz radio continuum map from the Australian Square Kilometer Array Pathfinder, and optical images of the Magellanic Cloud Emission Line Survey. Results. We detect significant emission from thermal plasma with kT = 0.2 keV in all the regions. There is also an additional higher- temperature emission component from a plasma with kT ≈ 0.7 keV. The surface brightness of this component is one order of magnitude lower than that of the lower-temperature component. In addition, non-thermal X-ray emission is significantly detected in the superbubble 30 Dor C. The absorbing column density NH in the LMC derived from the analysis of the X-ray spectra taken with eROSITA is consistent with the NH obtained from the emission of the cold medium over the entire area. Neon abundance is enhanced in the regions in and around 30 Dor and SN 1987A, indicating that the ISM has been chemically enriched by the young stellar population. In the centre of 30 Dor, there are two bright extended X-ray sources, which coincide with the stellar cluster RMC 136 and the Wolf-Rayet stars RMC 139 and RMC 140. For both regions the emission is best modelled with a high-temperature (kT > 1 keV) non-equilibrium ionisation plasma emission and a non-thermal component with a photon index of Γ = 1.3. In addition, we detect an extended X-ray source at the position of the optical SNR candidate J0529-7004 with thermal emission, and thus confirm its classification as an SNR. Conclusions. Using data from the early observations of the regions around SN 1987A and SNR N132D with eROSITA we confirm that there is thermal interstellar plasma in the entire observed field. eROSITA with its large field of view and high sensitivity at lower X-ray energies allows us for the first time to carry out a detailed study of the ISM at high energies consistently over a large region in the LMC. We thus measure the properties of the interstellar plasma and the distribution of non-thermal particles and derive the column density of the cold matter on the line of sight.

Position dispersive X-ray fluorescence

A novel scanning-free wavelength dispersive X-ray fluorescence spectrometer has been developed by combining low power X-ray tubes with X-ray optics. The X-rays are focused to a single point on the sample and then dispersed onto a flat diffracting crystal where they are spread depending on their energy through Bragg's law of diffraction onto a silicon strip detector. Throughout this study, the proposed method is referred to as Position Dispersive X-ray Fluorescence (PDXRF). The X-ray emission spectra of vanadium and copper as well as, CuO, CuS2 and V2O5 were measured. In the spectrometer energy resolutions of 3.14 eV and 8.94 eV FWHM were measured for V and Cu when measuring over a range of 4.8–5.8 keV and 6.2–9.1 keV respectively. The Kβ line shapes were fitted with a series of Voigt profiles and the energies and intensities of the Kβ valence transition peak, Kβ2,5, were determined. There was also sufficient variation in the intensity ratio of Kβ2,5/Kβ1,3 that the oxygen and sulphur compounds of V and Cu could be successfully observed and measured. The result demonstrates that this experimental setup is capable of measuring the Kβ line shape at resolutions of a few eV, allowing for chemical state analysis to be performed on 3d transition metals and their compounds such as the measurement of redox reactions to aid in battery development.

Preparation, structure and optical properties of mixed stacked cocrystals of 2,2':6′,2″-Terpyridine and 1,2,4,5-tetracyanobenzene

Organic charge-transfer cocrystals exhibit fantastic physical properties owning to their multi-component synergistic and collective effect. In spite of the abundant material supplies, the cocrystals people prepared so far are far less than expectation. Here, we reported the preparation, structure and optical properties of a mixed stacked cocrystal of 2,2':6′,2″-terpyridine and 1,2,4,5-tetracyanobenzene. The structural and optical properties were analyzed by using single-crystal X-ray diffraction (SCXRD), FTIR, Raman, optical absorption and emission spectra experimentally and the molecular electrostatic potential (MEP), Hirshfeld surface, the reduced density gradient (RDG), frontier molecular orbitals (FMO) theory, inter-fragment charge transfer (IFCT) analysis and time dependent density functional theory (TD-DFT) theoretically. The TTC sample exhibits strong up-conversion luminescence that is absent in their individual components. Theoretical analysis indicates that the NLO properties of TTC may be due to a significant increase in two-photon transition probabilities δTPA related to intermolecular charge transfer (CT) interactions. Our results may be helpful for a better understanding of NLO mechanism in ground state CT cocrystals.

Luminescent characteristics of Tm3+/Tb3+/Eu3+ tri-doped Na5Y9F32 single crystals for white emission with high thermal stability

By using an improved Bridgman method, 0.3 mol% Tm3+/0.6 mol% Tb3+/y mol% Eu3+ (y = 0, 0.4, 0.6, 0.8) doped Na5Y9F32 single crystals were prepared. The x-ray diffraction, excitation spectra, emission spectra and fluorescence decay curves were used to explore the crystal structure and optical performance of the obtained samples. When excited by 362 nm light, the cool white emission was realized by Na5Y9F32 single crystal triply-doped with 0.3 mol% Tm3+/0.6 mol% Tb3+/0.8 mol% Eu3+, in which the Commission Internationale de l’Eclairage (CIE) chromaticity coordinate was (0.2995, 0.3298) and the correlated color temperature (CCT) was 6586 K. The integrated normalized emission intensity of the tri-doped single crystal at 448 K could keep 62% of that at 298 K. The internal quantum yield (QY) was calculated to be ∼ 15.16% by integrating spheres. These results suggested that the single crystals tri-doped with Tm3+, Tb3+ and Eu3+ ions have a promising potential application for white light-emitting diodes (w-LEDs).

Study on luminescence properties of Tm3+/Tb3+/Eu3+ doped germanosilicate glass

In this paper, Tm3+/Tb3+/Eu3+ co-doped germanosilicate glass was prepared by high temperature melting method. The luminescence properties of the glass samples were characterized by X-ray diffraction, excitation and emission spectra, fluorescence lifetime and CIE chromaticity diagram. The density was measured and the distance between rare earth ions was calculated. The energy transfer method between Tm3+/Tb3+/Eu3+ is described in detail by Dexter theory. The results show that Tm3+ transfers energy to Tb3+. Tm3+ transfers energy to Eu3+ and the transfer mechanism is electric dipole-quadrupole transmission. Tb3+ transfers energy to Eu3+ in a electric quadrupole-quadrupole mechanism. The CIE chromaticity diagram shows that the prepared glasses are all in the white light range when the excitation wavelength is 359 nm, realizing the tunability from cool white light to warm white light.

Determination of Band Structure of Naturally Occurring Goethite with Al Substitution: A Case Study of Zhushan Iron Zone.

The photocatalytic property of Fe oxide minerals has long been considered to play an important role in shaping modern terrestrial environments. However, due to the complexity of natural settings, a precise determination of the band structure of natural goethite has not been achieved. In this work, the mineralogical characteristics of natural goethite samples obtained from Zhushan, China, were systematically studied through X-ray diffraction, transmission electron microscopy, X-ray energy dispersive spectroscopy, and X-ray fluorescence spectroscopy. Afterward, the band structure for both natural and synthetic goethite samples was determined by synchrotron-based X-ray absorption and emission spectra and photoelectron spectroscopy. The band gap of natural goethite (2.25 eV) was narrower than that of its synthetic counterpart (2.55 eV), and the valence band position of natural goethite was slightly lifted (−5.06 eV) compared to that of synthetic goethite (−5.38 eV). Al doping in natural goethite crystal, as revealed by the mineralogical tests, was the main reason that contributed to this difference. The theoretical calculation showed the narrowed band gap was caused by the contribution of Al-2p orbits at the top of the valence band. Therefore, free electrons can be created under light irradiation with a shorter wavelength. The experiments showed that natural goethite can photo-catalytically degrade methyl orange, and the degradation efficiency was better (47.5%) than that of the synthetic goethite group (31.5%). This study, for the first time, revealed the band structure and confirmed the photocatalytic properties of natural goethite, which should play an important role in surface substance evolution and elemental cycling.

Carbon K-edge x-ray emission spectroscopy of gas phase ethylenic molecules

We report on the C K-edge x-ray absorption spectra and the resonant (RXES) and non-resonant (NXES) x-ray emission spectra of ethylene, allene and butadiene in the gas phase. The RXES and NXES show clear differences for the different molecules. Overall both types of spectra are more structured for ethylene and allene, than for butadiene. Using density functional theory–restricted open shell configuration interaction single calculations, we simulate the spectra with remarkable agreement with the experiment. We identify the spectral features as being due to transitions involving localised 1s orbitals. For allene, there are distinct spectral bands that reflect transitions predominantly from either the central or terminal carbon atoms. These results are discussed in the context of ultrafast x-ray studies aimed at detecting the passage through conical intersections in polyatomic molecules.