X-ray Emission Spectra Research Articles

Valence-band hybridization in sulphides.

The hybridization state in solids often defines the critical chemical and physical properties of a compound. However, it is difficult to spectroscopically detect and evaluate hybridization beyond just general fingerprint signatures. Here, the valence-band hybridization of metal d-derived bands (short: "metal d bands") in selected metal sulphides is studied with a combined spectroscopic and theoretical approach to derive deeper insights into the fundamental nature of such compounds. The valence bands of the studied sulphides are comprised of hybrid bands derived from the metal d, S 3s, and S 3p states. Employing S K and L2,3 X-ray emission spectroscopy and spectra calculations based on density functional theory, the degree of hybridization (i.e., the covalency) of these bands can be directly probed as a function of their relative energies. We find that the relative intensity of the "metal d band" features in the spectra scales with the inverse square of the energy separation to the respective sulfur-derived bands, which can be analytically derived from a simple two-orbital model. This study demonstrates that soft X-ray emission spectroscopy is a powerful tool to study valence state hybridization, in particular in combination with hard X-ray emission spectroscopy, promising a broad impact in many research fields.

Breakdown of the molecular orbital picture for X-ray emission of water

By measuring X-ray emission of the water molecule in liquid phase we establish a first example of K-shell X-ray emission spectra with strong breakdown of the molecular orbital picture. A complete splitting of the 2a1 peak into satellites is observed. A theoretical model with electronic configurations generated by coupled excitations/de-excitations, so-called semi-internal configuration interaction, captures the experimentally recorded features well. Differences with respect to the corresponding breakdown effect in ultraviolet photoelectron spectrum are highlighted. Molecular dynamics calculations indicate that solvent broadening can only make up for a small fraction of the width of the recorded 2a1 derived band.

Statistical data analysis of x-ray spectroscopy data enabled by neural network accelerated Bayesian inference.

Bayesian inference applied to x-ray spectroscopy data analysis enables uncertainty quantification necessary to rigorously test theoretical models. However, when comparing to data, detailed atomic physics and radiation transfer calculations of x-ray emission from non-uniform plasma conditions are typically too slow to be performed in line with statistical sampling methods, such as Markov Chain Monte Carlo sampling. Furthermore, differences in transition energies and x-ray opacities often make direct comparisons between simulated and measured spectra unreliable. We present a spectral decomposition method that allows for corrections to line positions and bound-bound opacities to best fit experimental data, with the goal of providing quantitative feedback to improve the underlying theoretical models and guide future experiments. In this work, we use a neural network (NN) surrogate model to replace spectral calculations of isobaric hot-spots created in Kr-doped implosions at the National Ignition Facility. The NN was trained on calculations of x-ray spectra using an isobaric hot-spot model post-processed with Cretin, a multi-species atomic kinetics and radiation code. The speedup provided by the NN model to generate x-ray emission spectra enables statistical analysis of parameterized models with sufficient detail to accurately represent the physical system and extract the plasma parameters of interest.

Analyzing the Elements of X-ray Emission Spectrum of C/1999 S4 (LINEAR) and 9p/ Tempel 1 Comets

The study focused on the elemental abundance of two different comets. These comets were observed at an energy range of (100-10000) eV. The X-ray emission spectrum was analyzed and the results showed that comet C/1999 S4 (LINEAR) from the Oort cloud region (long-period) and comet 9p/Tempel 1 from the Kuiper Belt region (short-period) had the highest abundances of the different elements. The ds9 program used data from NASA's Chandra analysis to show the spectra of these comets and analyze their elements. The results showed that some elements were similar in all comets, such as (Carbon (C), Oxygen (O), Neon (Ne), and Silicon (Si)). While others varied from one comet to another, such as (Magnesium (Mg) and Chlorine (Cl)) elements which appeared in the C/1999 S4 (LINEAR) comet, and (Aluminum (A) and Phosphors (P)) elements which appeared in the 9P/Tempel 1 comet. This is due to these comets' areas of presence, where the elements of comets can be classified through their areas of presence.

Intermediate valence behavior of the ternary cerium-nickel-phosphide Ce2Ni12P5

The crystal structure of the ternary phosphide Ce2Ni12P5 (La2Ni12P5-type structure) has been determined from X-ray powder diffraction data: full profile refinement, monoclinic symmetry, space group P21/m, a = 10.7809(2) Å, b = 3.6869(1) Å, c = 13.1490(3) Å, β = 107.776(4)º, RI = 0.068, RP = 0.044, RwP = 0.060. Ce2Ni12P5 is a ferromagnet with a Curie temperature of 5.8(5) K. A significant deviation from the linearity of the temperature dependence of the electrical resistance for Ce2Ni12P5 has been found. The low-temperature part of the electrical resistance indicates the presence of magnetic interactions in Ce2Ni12P5. The influence of a magnetic field on the electrical resistance of Ce2Ni12P5 has been studied. The X-ray absorption spectrum at the Ce LIII edge and X-ray emission spectra of Ni and P at the K and LIII edges have been studied experimentally and theoretically using DFT+U calculations. The calculations show good agreement with the experimental measurements. The effective valence of Ce in Ce2Ni12P5 determined based on the Ce LIII absorption spectrum is ϑeff ∼ 3.05.

X-ray emission spectrum for axion–photon conversion in magnetospheres of strongly magnetized neutron stars

Detecting axionic dark matter (DM) could be possible in an X-ray spectrum from strongly magnetized neutron stars (NSs). We examine the possibility of axion–photon conversion in the magnetospheres of strongly magnetized NSs. In the current work, we investigate how the modified Tolman–Oppenheimer–Volkoff (TOV) system of equations (in the presence of a magnetic field) affects the energy spectrum of axions and axions-converted-photon flux. We have considered the distance-dependent magnetic field in the modified TOV system of equations. We employ three different equations of states (EoSs), namely APR, FPS, and SLY, to solve these equations. We obtain the axions emission rate by including the Cooper-pair-breaking formation process and Bremsstrahlung process in the core of NSs using the NSCool code. We primarily focus on Magnificient seven (M7) star RXJ 1856.5-3754. We further investigate the impact of the magnetic field on the actual observables, such as axion energy spectrum and axion-converted-photon flux at an axion mass in meV range by assuming mass MNS∼1.4M⊙.\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$M_{NS} \\sim 1.4M_{\\odot }.$$\\end{document} We compare our calculated axion-converted-photon flux from all available archival data sets from PN+MOS+Chandra. We also study the variation of the energy spectrum at a fixed energy with varying central magnetic fields. Our predicted axion-converted-photon flux values as a function of axion energy closely follow the experimentally archival data, which allows us to put bounds on the axion mass for the three EoS.

QUANTUM CHEMICAL STUDY OF THE ELECTRONIC STRUCTURE OF YTTERBIUM HALIDES

The study of ytterbium halide crystals using the compound-tunable embedding potential (CTEP) method is carried out in the framework of the density functional theory. For subsequent calculations using the coupled-cluster methods, the optimization of atomic bases is carried out, and for this purpose stochiometric molecular systems were studied. The chemical shift of the lines of the X-ray emission spectrum, Kα1 and Kα2, in YbHal3 relative to YbHal2 was chosen as a criterion for verifying the computational accuracy of the properties localized on the nucleus of a heavy atom, Yb, since this method is a unique tool for analyzing partial electron densities near a heavy nucleus speci cally for compounds of d- and f-elements. In the study, ve main versions for the halogen basis set sizes were considered. The stability of the results was obtained using the CCSD and CCSD(T) coupled cluster methods for molecular systems YbF2, YbF3, YbCl2, YbCl3.

TDDFT and the x-ray absorption spectrum of liquid water: Finding the "best" functional.

We investigate the performance of time-dependent density functional theory (TDDFT) for reproducing high-level reference x-ray absorption spectra of liquid water and water clusters. For this, we apply the integrated absolute difference (IAD) metric, previously used for x-ray emission spectra of liquid water [T. Fransson and L. G. M. Pettersson, J. Chem. Theory Comput. 19, 7333-7342 (2023)], in order to investigate which exchange-correlation (xc) functionals yield TDDFT spectra in best agreement to reference, as well as to investigate the suitability of IAD for x-ray absorption spectroscopy spectrum calculations. Considering highly asymmetric and symmetric six-molecule clusters, it is seen that long-range corrected xc-functionals are required to yield good agreement with the reference coupled cluster (CC) and algebraic-diagrammatic construction spectra, with 100% asymptotic Hartree-Fock exchange resulting in the lowest IADs. The xc-functionals with best agreement to reference have been adopted for larger water clusters, yielding results in line with recently published CC theory, but which still show some discrepancies in the relative intensity of the features compared to experiment.

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.

Development of the multiplex imaging chamber atPAL-XFEL.

Various X-ray techniques are employed to investigate specimens in diverse fields. Generally, scattering and absorption/emission processes occur due to the interaction of X-rays with matter. The output signals from these processes contain structural information and the electronic structure of specimens, respectively. The combination of complementary X-ray techniques improves the understanding of complex systems holistically. In this context, we introduce a multiplex imaging instrument that can collect small-/wide-angle X-ray diffraction and X-ray emission spectra simultaneously to investigate morphological information with nanoscale resolution, crystal arrangement at the atomic scale and the electronic structure of specimens.

An improved methodology for modeling short pulse buried layer x-ray emission spectra

Radiation-hydrodynamic and spectroscopic modeling are important aspects of high energy density experimental design. In this paper, we improve the performance and capabilities over those obtainable with a previous methodology used for simulating x-ray emission spectra from buried layer targets heated by short pulse lasers. The improvement incorporates post-processing HYDRA radiation-hydrodynamic output with a non-local thermodynamic equilibrium atomic-kinetics radiation transport code, Cretin. Each code uses an independent radiation field which allows decoupling HYDRA's radiation group structure from Cretin's spectral output to improve the speed and flexibility of the design methodology. The execution time decreases from 2–3 days to a few hours while the flexibility of the improved methodology allows for performing sensitivity studies including a comparison of steady-state and time-dependent atomic kinetics and differences in the radiation group structure.

Simple derivation of L-absorption spectra of 3d transition metal elements by the self-absorption effect observed in soft X-ray emission spectra.

This study proposes a simple evaluation method for deriving L-absorption information from two L-emission spectra of 3d transition metal (TM) elements obtained at two different accelerating voltages. This method realizes a spatial identity for X-ray emission and absorption spectroscopies. This method was evaluated for the Fe L-emission spectra of Fe and its oxides and was applied to the TM L-emission spectra of MnO, Co, CoO and NiO. The derived absorption peak positions were consistent with those obtained previously at synchrotron orbital radiation facilities, which considered the core-hole effect. This simple derivation method could be useful for obtaining X-ray absorption spectroscopy distribution images from X-ray emission spectroscopy mapping data obtained by scanning electron microscopy.

Understanding the X-ray emission spectrum after excitation with a source of X-rays: From theory to experiment

The modified Boltzmann-Chandrasekhar equation of transport for photons is the proper framework for describing the photon radiation field with a complete description of the polarization state. The characterization of the radiation field requires a detailed knowledge of the interactions of photons with mater and comprises also the contribution of the secondary electrons to the photon field through mechanisms like inner impact ionization and bremsstrahlung. It will be shown a solution obtained without the need of solving the coupled transport electrons-photons. With all these interactions, the theoretical characterization of the X-ray spectrum of emission after excitation with a source of X-rays can be straightforwardly obtained from the albedo solution to the equation. In this work it will be privileged a Monte Carlo (MC) solution. However, this solution is still far from an experimental measurement modified by the radiation detection devices, comprised the pulse electronics. In this work we put together a MC simulation able to get a detailed transport solution and a complete characterization of the contributions of the detection chain. It is discussed the influence of the single contributions and how they combine to make that a simulated X-ray spectrum matches well a real measurement.

Evaluating the Impact of the Tamm-Dancoff Approximation on X-ray Spectrum Calculations.

The impact of the Tamm-Dancoff approximation (TDA) for time-dependent density functional theory (TDDFT) calculations of X-ray absorption and X-ray emission spectra (XAS and XES) is investigated, showing small discrepancies in the excitation energies and intensities. Through explicit diagonalization of the TDDFT Hessian, XES was considered by using full TDDFT with a core-hole reference state. This has previously not been possible with most TDDFT implementations as a result of the presence of negative eigenvalues. Furthermore, a core-valence separation (CVS) scheme for XES is presented, in which only elements including the core-hole are considered, resulting in a small Hessian with the dimension of the number of remaining occupied orbitals of the same spin as the core-hole (CH). The resulting spectra are in surprisingly good agreement with the full-space counterpart, illustrating the weak coupling between the valence-valence and valence-CH transitions. Complications resulting from contributions from the discretized continuum are discussed, which can occur for TDDFT calculations of XAS and XES and for TDA calculations of XAS. In conclusion, we recommend that TDA be used when calculating X-ray emission spectra, and either CVS-TDA or CVS-TDDFT can be used for X-ray absorption spectra.

High-brightness red-emitting Eu3+-activated Ca2LuZr2Al3O12 garnet phosphors with excellent thermal stability for near-UV-pumped white LEDs

In this work, a group of red-emitting Ca2LuZr2Al3O12:xEu3+ (x = 20%, 30%, 40%, 50%, 60%, 70% and 80%) phosphors have been prepared and their luminescence properties are studied. X-ray diffraction, excitation and emission spectra, fluorescence decay curves, CIE color coordinates, and temperature-dependent photoluminescence spectra are used to characterize these samples. All these Ca2LuZr2Al3O12:Eu3+ compounds exhibit intense red luminescence peaking at around 618 nm under 394 nm excitation. The critical concentration of Eu3+ ion is 50 mol%, and the concentration quenching mechanism has been discussed and analyzed. The CIE color coordinates of the optimal Ca2LuZr2Al3O12:50%Eu3+ sample are (0.6506, 0.3487), and it has a high color purity of 90.7%. Importantly, the emission intensity of Ca2LuZr2Al3O12:50%Eu3+ is about 1.67 times higher compared to the commercial Y2O3:Eu3+ red phosphor. What's more, Ca2LuZr2Al3O12:50%Eu3+ phosphor also displays excellent resistance to thermal quenching at elevated temperature; only 14% emission intensity is lost at 150 °C.

Attosecond-pump attosecond-probe x-ray spectroscopy of liquid water.

Attosecond-pump/attosecond-probe experiments have long been sought as the most straightforward method for observing electron dynamics in real time. Although there has been much success with overlapped near-infrared femtosecond and extreme ultraviolet attosecond pulses combined with theory, true attosecond-pump/attosecond-probe experiments have been limited. We used a synchronized attosecond x-ray pulse pair from an x-ray free-electron laser to study the electronic response to valence ionization in liquid water through all x-ray attosecond transient absorption spectroscopy (AX-ATAS). Our analysis showed that the AX-ATAS response is confined to the subfemtosecond timescale, eliminating any hydrogen atom motion and demonstrating experimentally that the 1b1 splitting in the x-ray emission spectrum is related to dynamics and is not evidence of two structural motifs in ambient liquid water.

X-ray production cross sections for Ir and Bi M-subshells induced by electron impact

M-subshell X-ray production cross sections were indirectly measured for Ir and Bi targets irradiated with monoenergetic electron beams. The projectile energy range ran from 2.2 to 28 keV, impinging on Ir and Bi pure bulk targets in a scanning electron microscope. The resulting X-ray emission spectra were acquired with an energy dispersive spectrometer, and processed afterwards by means of a robust parameter optimization procedure developed previously. X-ray production cross sections were finally obtained through an approach involving an analytical prediction for the emission spectra, which relies on the ionization depth distribution function. The values obtained by this approach were compared with empirical and theoretical predictions, appealing to different relaxation data taken from the literature.

Structural descriptors and information extraction from X-ray emission spectra: aqueous sulfuric acid.

Machine learning can reveal new insights into X-ray spectroscopy of liquids when the local atomistic environment is presented to the model in a suitable way. Many unique structural descriptor families have been developed for this purpose. We benchmark the performance of six different descriptor families using a computational data set of 24 200 sulfur Kβ X-ray emission spectra of aqueous sulfuric acid simulated at six different concentrations. We train a feed-forward neural network to predict the spectra from the corresponding descriptor vectors and find that the local many-body tensor representation, smooth overlap of atomic positions and atom-centered symmetry functions excel in this comparison. We found a similar hierarchy when applying the emulator-based component analysis to identify and separate the spectrally relevant structural characteristics from the irrelevant ones. In this case, the spectra were dominantly dependent on the concentration of the system, whereas adding the second most significant degree of freedom in the decomposition allowed for distinction of the protonation state of the acid molecule.

Core-to-core X-ray emission spectra from Wannier based multiplet ligand field theory

Recent advances using Density Functional Theory (DFT) to augment Multiplet Ligand Field Theory (MLFT) have led to ab-initio calculations of many formerly empirical parameters. This development makes MLFT more predictive instead of interpretive, thus improving its value for studies of highly correlated 3d, 4d, and f-electron systems. Synchrotron time is always at a premium, and tools that provide predictive capabilities have clear value when it comes to planning studies. Here, we develop a DFT + MLFT based approach for core-to-core Kα x-ray emission spectra (XES) and evaluate its performance for a range of transition metal systems. We find good agreement between theory and experiment, as well as the ability to capture key spectral trends related to spin and oxidation state. We also discuss limitations of the model in the context of the remaining free parameters and suggest directions forward.

Natural linewidths of Cu Kα1,2 spectra obtained with an antiparallel double-crystal X-ray spectrometer

An investigation of Cu Kα X-ray emission spectra, together with their satellite lines, using both experimental techniques and theoretical calculations, provides accurate values for the natural linewidths and other parameters of the emission lines.