3p-3d Transitions Research Articles

Analysis of the extreme ultraviolet broadband spectral characteristics and spatiotemporal evolution of laser-produced germanium plasmas

This paper presents comprehensive spectral measurements and a theoretical analysis of laser-produced germanium (Ge) plasma within the 7.5–17 nm wavelength range, with the measurements being performed using spatiotemporally-resolved emission spectroscopy. We obtained and analyzed the extreme ultraviolet (EUV) spectra and their variations meticulously at various positions adjacent to the target surface. The 3p and 3d excitations of Ge ions spanning from Ge4+ to Ge13+ were calculated using the Cowan configuration interaction codes, with particular emphasis being placed on analysis of the spectral line distributions in the 3d-np, 3d-nf, and 3p-3d, 4s, 4d transition arrays. This analysis indicated the contributions made by these transition arrays to the broadband spectral features that were observed experimentally. By using a steady-state collisional radiation model along with a normalized Boltzmann distribution assumption, we clarified the predominant contributions of the 3d-4p and 3p-3d transitions from the Ge7+ to Ge9+ ions in close proximity to the target surface, along with those from the Ge5+ and Ge6+ ions at greater distances. Furthermore, by combining the results above with a plasma dynamics evolution analysis, we gained insights into how the plasma's transient and nonuniform properties influence the analysis of complex EUV band spectral profiles and examine their implications for spectral diagnostics. These results will be useful for plasma spectral diagnosis and for application to development of pulsed short-wavelength light sources.

Measurement of 2p-3d absorption in a hot molybdenum plasma

We present measurements of the 2p-3d transition opacity of a hot molybdenum–scandium sample with nearly half-vacant molybdenum M-shell configurations. A plastic-tamped molybdenum–scandium foil sample is radiatively heated to high temperature in a compact D-shaped gold Hohlraum driven by ∼30 kJ laser energy at the SG-100 kJ laser facility. X rays transmitted through the molybdenum and scandium plasmas are diffracted by crystals and finally recorded by image plates. The electron temperatures in the sample in particular spatial and temporal zones are determined by the K-shell absorption of the scandium plasma. A combination of the IRAD3D view factor code and the MULTI hydrodynamic code is used to simulate the spatial distribution and temporal behavior of the sample temperature and density. The inferred temperature in the molybdenum plasma reaches a average of 138 ± 11 eV. A detailed configuration-accounting calculation of the n = 2–3 transition absorption of the molybdenum plasma is compared with experimental measurements and quite good agreement is found. The present measurements provide an opportunity to test opacity models for complicated M-shell configurations.

Extreme ultraviolet spectral characteristic analysis of highly charged ions in laser-produced Cu plasmas

This paper reports the results of spectral measurements and a theoretical analysis of the temporal and spatial evolution of laser-produced Cu plasma in vacuum in the range of 8–14 nm. The time dependence of the extreme ultraviolet band spectrum at different positions near the target surface was obtained and found to be dominated by three broad-band features. The 3p and 3d excitations of Cu5+–Cu9+ ions were calculated using the Hartree–Fock theory with configuration interactions. The characteristics of the spectral line distribution for the 3p–nd and 3d–nf transition arrays were analyzed. Based on the steady-state collisional radiation model and the normalized Boltzmann distribution, the complex spectral structure in the band of 13–14 nm is accurately explained through consistency comparisons and benchmarking between the experimental and theoretical simulation spectra, demonstrating that the structure mainly stems from the overlapping contribution of the 3d–4f and 3p–3d transition arrays for the Cu5+–Cu9+ ions. These results may help in studying the radiation characteristics of isoelectronic series highly-charged ions involving the 3d excitation process.

Experimental and theoretical investigation of EUV radiation behavior of laser-produced Zr plasmas

Extreme ultraviolet radiation of laser-produced zirconium (Zr) plasmas were measured in the 6.7–14.7 nm region using a spatio-temporally resolved laser-produced plasma spectroscopy technique. At shorter wavelengths, the spectrum was dominated by several lines attributed to the 4s-(6p,7p,8p) transition arrays of Zr6+ to Zr10+ ions. For the 4s-5p and 4p-6 s transitions, the spectral lines concentrated near 11.18 nm and smoothly move towards longer wavelengths with decreasing ion-charge-state, which are experimentally and theoretically investigated. The Hartree-Fok (HF) method with relativistic corrections (HFR) using the Cowan's codes and Flexible Atomic Code (FAC) were used to calculate and interpret the observed spectra, respectively. At relatively high temperatures, lines from 3p-3d transitions in Zr13+ and Zr14+ ions have been found to have an important contribution. A number of spectral lines are established in this study for the first time. Besides the atomic structure calculations, a numerical computation based on the assumption of a normalized Boltzmann distribution among the excited states associated with a steady-state collisional-radiative model (CR), has also been performed to obtain the plasma parameters by comparing the experimental and simulated spectra. The corresponding dominant ion stages and ion fractions for different ion stages were obtained. We have also provided the evolution of rate coefficients as a function of electron density and electron temperature. We reproduced synthetic spectra which are in good agreement with the experiment. Temporal and spatial evolution behavior about plasma parameters have been analyzed. The variation of electron plasma frequency and skin depth with plasma temperature were introduced. The results may be beneficial for spectroscopic diagnostics of hot plasmas in tokamak and fusion research.

Resonance enhancement of harmonics in the vicinity of 32 nm spectral range during propagation of femtosecond pulses through the molybdenum plasma

We demonstrate the enhancement of harmonics in the vicinity of 32 nm while generating them in the Mo laser-produced plasma. The enhanced harmonics centered at around the 25th harmonic of 806 nm radiation were analyzed by different means (delay between heating and driving pulses, dependences of harmonic yield on the driving and heating pulse intensities and durations, different regimes of plasma formation, two-color pump of plasma, application of chirped pulses, etc). The role of strong ionic transition possessing large oscillator strength leading to the growth of the nonlinear optical response is discussed. Comparative studies using molybdenum, silver, and chromium laser-produced plasmas are presented. To validate the experimental findings, we numerically simulate harmonic generation from Mo using full-dimensional, all-electron, first-principles calculations. The calculated harmonic spectra exhibit a prominent peak around 32 nm and a suppression around 36–38 nm, successfully reproducing the experimentally observed features. Our transition-resolved analyses of the calculation results reveal both that the 4p-4d transitions are responsible for the observed enhancement and that the destructive interference between the 4p-4d transitions and the recombination to the 4d orbitals leads to the observed suppression.

Revisiting the Fe xvii Line Emission Problem: Laboratory Measurements of the 3s–2p and 3d–2p Line-formation Channels

Abstract We determined relative X-ray photon emission cross sections in Fe xvii ions that were mono-energetically excited in an electron beam ion trap. Line formation for the 3s (3s−2p) and 3d (3d−2p) transitions of interest proceeds through dielectronic recombination (DR), direct electron-impact excitation (DE), resonant excitation (RE), and radiative cascades. By reducing the electron-energy spread to a sixth of that of previous works and increasing counting statistics by three orders of magnitude, we account for hitherto unresolved contributions from DR and the little-studied RE process to the 3d transitions, and also for cascade population of the 3s line manifold through forbidden states. We found good agreement with state-of-the-art many-body perturbation theory (MBPT) and the distorted-wave (DW) method for the 3s transition, while in the 3d transitions known discrepancies were confirmed. Our results show that DW calculations overestimate the 3d line emission due to DE by ∼20%. Inclusion of electron-electron correlation effects through the MBPT method in the DE cross-section calculations reduces this disagreement by ∼11%. The remaining ∼9% in 3d and ∼11% in 3s/3d discrepancies are consistent with those found in previous laboratory measurements, solar, and astrophysical observations. Meanwhile, spectral models of opacity, temperature, and turbulence velocity should be adjusted to these experimental cross sections to optimize the accuracy of plasma diagnostics based on these bright soft X-ray lines of Fe xvii.

A zone-plate-based two-color spectrometer for indirect X-ray absorption spectroscopy.

X-ray absorption spectroscopy (XAS) is a powerful element-specific technique that allows the study of structural and chemical properties of matter. Often an indirect method is used to access the X-ray absorption (XA). This work demonstrates a new XAS implementation that is based on off-axis transmission Fresnel zone plates to obtain the XA spectrum of La0.6Sr0.4MnO3 by analysis of three emission lines simultaneously at the detector, namely the O 2p-1s, Mn 3s-2p and Mn 3d-2p transitions. This scheme allows the simultaneous measurement of an integrated total fluorescence yield and the partial fluorescence yields (PFY) of the Mn 3s-2p and Mn 3d-2p transitions when scanning the Mn L-edge. In addition to this, the reduction in O fluorescence provides another measure for absorption often referred to as the inverse partial fluorescence yield (IPFY). Among these different methods to measure XA, the Mn 3s PFY and IPFY deviate the least from the true XA spectra due to the negligible influence of selection rules on the decay channel. Other advantages of this new scheme are the potential to strongly increase the efficiency and throughput compared with similar measurements using conventional gratings and to increase the signal-to-noise of the XA spectra as compared with a photodiode. The ability to record undistorted bulk XA spectra at high flux is crucial for future in situ spectroscopy experiments on complex materials.

Simultaneous X-ray and XUV absorption measurements in nickel laser-produced plasma close to LTE

We present an experiment performed in 2016 at the LULI2000 laser facility in which X-ray and XUV absorption structures of nickel hot plasmas were measured simultaneously. Such experiments may provide stringent tests of the accuracy of plasma atomic-physics codes used to the modeling of plasmas close to local thermodynamic equilibrium. The experimental set-up relies on a symmetric heating of the sample foil by two gold hohlraums in order to reduce the spatial gradients. The plasma conditions are characterized by temperatures between 10 and 20 eV and densities of the order of 10−3 g/cm3–10−2 g/cm3. For the X-ray part, we investigate the 2p-3d and 2p-4d transitions, and for the XUV part, we recorded the Δn = 0 (n = 3) transitions, which present a high sensitivity to plasma temperature. These latter transitions are of particular interest because, in mid-Z plasmas, they dominate the Planck and Rosseland mean opacities. Measured spectra are compared to calculations performed using the hybrid opacity code SCO-RCG and the Flexible Atomic Code (FAC). The influence of a spectator electron on the calculated spectra is analyzed using the latter code.

Cr L-Edge X-ray Absorption Spectroscopy of CrIII(acac)3 in Solution with Measured and Calculated Absolute Absorption Cross Sections.

X-ray absorption spectroscopy at the L-edge of 3d transition metals is widely used for probing the valence electronic structure at the metal site via 2p-3d transitions. Assessing the information contained in L-edge absorption spectra requires systematic comparison of experiment and theory. We here investigate the Cr L-edge absorption spectrum of high-spin chromium acetylacetonate CrIII(acac)3 in solution. Using a transmission flatjet enables determining absolute absorption cross sections and spectra free from X-ray-induced sample damage. We address the challenges of measuring Cr L absorption edges spectrally close to the O K absorption edge of the solvent. We critically assess how experimental absorption cross sections can be used to extract information on the electronic structure of the studied system by comparing our results of this CrIII (3d3) complex to our previous work on L-edge absorption cross sections of MnIII(acac)3 (3d4) and MnII(acac)2 (3d5). Considering our experimental uncertainties, the most insightful experimental observable for this d3(CrIII)-d4(MnIII)-d5(MnII) series is the L-edge branching ratio, and we discuss it in comparison to semiempirical multiplet theory and ab initio restricted active space calculations. We further discuss and analyze trends in integrated absorption cross sections and correlate the spectral shapes with the local electronic structure at the metal sites.

Absolute Photoionization Cross Section for Fe6+ to Fe10+ Ions in the Photon Energy Region of the 2p–3d Resonance Lines

Abstract Resonant single photoionization cross sections of Fen+ (n = 6 to 10) ions have been measured in absolute values using a merged-beams setup at the SOLEIL synchrotron radiation facility. Photon energies were between about 710 and 780 eV, covering the range of the 2p–3d transitions. The experimental cross sections are compared to calculations we performed using a multi-configuration Dirac–Fock code and the OPAS code dedicated to radiative opacity calculations. Comparisons are also done with the Chandra X-ray observatory NGC 3783 spectra and with the results of previously published calculations.

Resonant Electron Impact Excitation of 3d Levels in Fe14+ and Fe15+

Abstract We present laboratory spectra of the 3p–3d transitions in Fe14+ and Fe15+ excited with a mono-energetic electron beam. In the energy-dependent spectra obtained by sweeping the electron energy, resonant excitation is confirmed as an intensity enhancement at specific electron energies. The experimental results are compared with theoretical cross sections calculated based on fully relativistic wave functions and the distorted wave approximation. Comparisons between the experimental and theoretical results show good agreement for the resonance strength. A significant discrepancy is, however, found for the non-resonant cross section in Fe14+. This discrepancy is considered to be the fundamental cause of the previously reported inconsistency of the model with the observed intensity ratio between the and transitions.

Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers.

X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn ∼ 6–15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions.

Analysis of spectra of 3s-3p and 3p-3d transitions of highly-charged copper ions

Beam-foil excited spectra in the range of 160–360 Å from highly charged copper ions were identified with the aid of the National Institute of Standards and Technology Atomic Spectra Database and theoretical calculations with Cowan and Flexible Atomic Code (FAC) calculations. Spectra arising from 3s-3p and 3p-3d transitions of Cu13+–Cu22+ ions were considered. The ion fraction at an ion beam energy of 110 MeV was estimated from the equilibrium charge distribution of the fast ion beams after passing through the solid. The corresponding simulated spectra were in good agreement with the experimental result. Our Cowan and FAC calculation results should be useful for further spectral identification and lifetime measurements of highly charged copper ions.

Calculation of Rates of 4p–4d Transitions in Ar II

Recent experimental work by Belmonte et al. (2014) has given rates for some 4p–4d transitions that are significantly at variance with the previous experimental work of Rudko and Tang (1967) recommended in the NIST tabulations. To date, there are no theoretical rates with which to compare. In this work, we provide such theoretical data. We have undertaken a substantial and systematic configuration interaction calculation, with an extrapolation process applied to ab initio mixing coefficients, which gives energy differences in agreement with experiment. The length and velocity forms give values that are within 10%–15% of each other. Our results are in sufficiently close agreement with those of Belmonte et al. that we can confidently recommend that their results are much more accurate than the early results of Rudko and Tang, and should be adopted in place of the latter.

Electronic structure of Mo1−xRex alloys studied through resonant photoemission spectroscopy

We studied the electronic structure of Mo-rich Mo1−xRex alloys () using valence band photoemission spectroscopy in the photon energy range 23–70 eV and density of states calculations. Comparison of the photoemission spectra with the density of states calculations suggests that, with respect to the Fermi level EF, the d states lie mostly in the binding energy range 0 to −6 eV, whereas s states lie in the binding energy range −4 to −10 eV. We observed two resonances in the photoemission spectra of each sample, one at about 35 eV photon energy and the other at about 45 eV photon energy. Our analysis suggests that the resonance at 35 eV photon energy is related to the Mo 4p–5s transition and the resonance at 45 eV photon energy is related to the contribution from both the Mo 4p–4d transition (threshold: 42 eV) and the Re 5p–5d transition (threshold: 46 eV). In the constant initial state plot, the resonance at 35 eV incident photon energy for binding energy features in the range EF (BE = 0) to −5 eV becomes progressively less prominent with increasing Re concentration x and vanishes for x > 0.2. The difference plots obtained by subtracting the valence band photoemission spectrum of Mo from that of Mo1−xRex alloys, measured at 47 eV photon energy, reveal that the Re d-like states appear near EF when Re is alloyed with Mo. These results indicate that interband s–d interaction, which is weak in Mo, increases with increasing x and influences the nature of the superconductivity in alloys with higher x.

XUV spectra of 2nd transition row elements: identification of 3d–4p and 3d–4f transition arrays

The use of laser produced plasmas (LPPs) in extreme ultraviolet/soft x-ray lithography and metrology at 13.5 nm has been widely reported and recent research efforts have focused on developing next generation sources for lithography, surface morphology, patterning and microscopy at shorter wavelengths. In this paper, the spectra emitted from LPPs of the 2nd transition row elements from yttrium (Z = 39) to palladium (Z = 46), with the exception of zirconium (Z = 40) and technetium (Z = 43), produced by two Nd:YAG lasers which delivered up to 600 mJ in 7 ns and 230 mJ in 170 ps, respectively, are reported. Intense emission was observed in the 2–8 nm spectral region resulting from unresolved transition arrays (UTAs) due to 3d–4p, 3d–4f and 3p–3d transitions. These transitions in a number of ion stages of yttrium, niobium, ruthenium and rhodium were identified by comparison with results from Cowan code calculations and previous studies. The theoretical data were parameterized using the UTA formalism and the mean wavelength and widths were calculated and compared with experimental results.

Element-specific characterization of transient electronic structure of solvated Fe(II) complexes with time-resolved soft X-ray absorption spectroscopy.

Polypyridyl transition-metal complexes are an intriguing class of compounds due to the relatively facile chemical designs and variations in ligand-field strengths that allow for spin-state changes and hence electronic configurations in response to external perturbations such as pressure and light. Light-activated spin-conversion complexes have possible applications in a variety of molecular-based devices, and ultrafast excited-state evolution in these complexes is of fundamental interest for understanding of the origins of spin-state conversion in metal complexes. Knowledge of the interplay of structure and valence charge distributions is important to understand which degrees of freedom drive spin-conversion and which respond in a favorable (or unfavorable) manner. To track the response of the constituent components, various types of time-resolved X-ray probe methods have been utilized for a broad range of chemical and biological systems relevant to catalysis, solar energy conversions, and functional molecular devices. In particular, transient soft X-ray spectroscopy of solvated molecules can offer complementary information on the detailed electronic structures and valence charge distributions of photoinduced intermediate species: First-row transition-metal L-edges consist of 2p-3d transitions, which directly probe the unoccupied valence density of states and feature lifetime broadening in the range of 100 meV, making them sensitive spectral probes of metal-ligand interactions. In this Account, we present some of our recent progress in employing picosecond and femtosecond soft X-ray pulses from synchrotron sources to investigate element specific valence charge distributions and spin-state evolutions in Fe(II) polypyridyl complexes via core-level transitions. Our results on transient L-edge spectroscopy of Fe(II) complexes clearly show that the reduction in σ-donation is compensated by significant attenuation of π-backbonding upon spin-crossover. This underscores the important information contained in transient metal L-edge spectroscopy on changes in the 3d orbitals including oxidation states, orbital symmetries, and covalency, which largely define the chemistry of these complexes. In addition, ligand K-edge spectroscopy reveals the "ligand view" of the valence charge density by probing 1s-2p core-level transitions at the K-edge of light elements such as nitrogen, carbon, and oxygen. In the case of Fe(II) spin-conversion complexes, additional details of the metal-ligand interactions can be obtained by this type of X-ray spectroscopy. With new initiatives in and construction of X-ray free-electron laser sources, we expect time-resolved soft X-ray spectroscopy to pave a new way to study electronic and molecular dynamics of functional materials, thereby answering many interesting scientific questions in inorganic chemistry and material science.

Polarization of Balmer alpha radiation resulting from H++H collisions in Debye plasmas

The linear polarization degree of Balmer alpha radiation resulting from H++H(1s) collisions in a hot, dense weakly coupled plasma is studied in the energy range 1–140 keV/u by adopting the Debye-Hückel potential to represent the screened interaction between charged plasma particles. Due to the energy splitting of nl hydrogen states in the short range Debye-Huckel potential, the Balmer alpha radiation contains three components corresponding to 3s-2p, 3p-2s, and 3d-2p transitions, of which only the last two can be linearly polarized. For calculation of 3lm excitation and electron capture cross sections, the two-center expansion atomic orbital close coupling method is used for a number of Debye screening lengths. The effects of plasma screening on the 3lm cross sections are manifested in significant changes of their magnitudes and energy behavior with respect to the ones in the unscreened case, producing significant changes in the polarization degree of Balmer 3p-2s and 3d-2p lines.

Characteristics of x-ray emission from optically thin high-Z plasmas in the soft x-ray region

The characteristics of soft x-ray emission from optically thin high-Z plasmas of gold, lead and bismuth were investigated with the large helical device. Compared to optically thicker laser-produced plasmas, significantly different spectral structures were observed due to the difference in opacities and electron temperatures. Peak structures appearing in unresolved transition arrays were identified by calculations using atomic structure codes. The main contributors of discrete line emission in each case were Pd-, Ag-, and Rh-like ion stages. The present calculations point to the overestimation of contributions for 4p–4d transitions based on intensity estimates arising purely from gA distributions that predict strong emission from 4p–4d transitions. Understanding of such spectral emission is not only important for the completion of databases of high-Z highly ion charge states but also the development of promising high brightness sources for biological imaging applications.

Radial profiles and emissivity ratio analysis of Ne-like FeXVII n = 3−2 transitions in Large Helical Device

The radial profiles of the FeXVII 3s-2p and 3d-2p transitions emitted in the wavelength range of 15 − 17 A have been observed in the Large Helical Device (LHD). The chord-integrated radial profiles are converted into radial emissivity profiles by means of Abel inversion. The emissivity ratios among FeXVII n = 3−2 transitions calculated from the radial emissivity profiles are compared with calculations based on a collisional-radiative (CR) model developed for Fe ions. The result reasonably confirms the effect of electron temperature and density on the emissivity ratio. However, the emissivity of the 3C (2p 53d 1 P 1 → 2p 6) transition is obviously lower than the prediction from the CR model. This discrepancy is consistent with measurements in the solar corona and other laboratory plasmas.