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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Advanced Simulation of ITER Core X-ray Crystal Spectroscopy

X-Ray Simulation Analysis (XRSA) is an analytical ray-tracing mixed code developed specifically for the ITER Core X-Ray Crystal Spectroscopy (XRCS-Core) diagnostic, which employs a dual-reflection configuration incorporating multiple pre-reflectors made of Highly Oriented Pyrolytic Graphite (HOPG) and spherically curved analyzing crystals. The ITER XRCS-Core is designed for high spectral resolution measurement in specific wavelength ranges, including narrow bands around 1.354 Å for W 64+ , 2.19 Å for Xe 51+ , and 2.555 Å for Xe 44+ and Xe 47+ , enabling diagnostic capability across a broad electron temperature range in the ITER plasma. XRSA facilitates efficient simulation of the spectral performance of this complex X-ray spectroscopic system. Recent updates to the XRSA code have incorporated two critical effects: auto-focusing, which specifically applies to HOPG, and polarization. These two effects are particularly important in the dual-reflection configuration used in the ITER XRCS-Core system to provide more accurate modeling results. Here, simulations conducted with the updated code demonstrate that polarization has a substantial impact on the performance of the dual-reflection system. Additionally, the combined influence of polarization and system layout introduces performance variations across channels through the same crystal.

Computer graphics↗
DOE OSTI2025

Performance characterization of x-ray crystal spectroscopy highly oriented pyrolytic graphite reflectors based on x-ray diffractometry experiments

The use of Highly Oriented Pyrolytic Graphite (HOPG) reflectors is often proposed in the design of X-ray Crystal Spectroscopy (XCS) diagnostic systems for the next-generation tokamak devices, including the ITER project. Here, this study introduces an experimental study based on the X-Ray Diffractometry (XRD) method to evaluate the performance of HOPG reflectors. The experimental method provides both the angular responses and the reflectivities of the HOPG reflectors. A demonstrative XRD experiment is conducted, and the details of the experiment are introduced. This method enables precise studies on HOPG reflectors, facilitating the design of XCS diagnostic systems for future tokamaks.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Identifying Order and Disorder in Double Four-Membered Rings via Raman Spectroscopy during Crystallization of LTA Zeolite

Fluoride (F – ) has been essential for the synthesis of low-defect siliceous zeolites. It has been hypothesized that F – balances the positive charges from organic structure-directing agents (OSDAs) and stabilizes key building units during zeolite crystallization such as the double four-membered ring (D4R). However, due to the lack of characterization techniques for investigating medium-range structures, including rings and cages formed during zeolite crystallization, the roles of F – in stabilizing building units and maintaining local charge balance during zeolite assembly are not yet fully understood. Here, the crystallization of siliceous Linde type A (LTA) zeolite in the presence of F – was investigated using Raman spectroscopy and periodic density functional theory (DFT) calculations. We have discovered that the F – -filled double four-membered ring (F – /D4R) and the empty D4R exhibit rather distinct Raman features. Both the F – /D4R and empty D4R are formed in the LTA zeolite synthesized in the presence of F – using 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the OSDA. Observed Raman bands of the F – /D4R and empty D4R, along with predictive DFT calculations on LTA supercells, reveal an ordered distribution of these two D4R units in the final as-made LTA zeolite. The discovery of these distinct Raman signatures of F – /D4R and empty D4R units opens an interesting new window for studying defects in the D4R during zeolite formation. In particular, we have observed variation in Raman intensities of F – /D4R and empty D4R bands during LTA crystallization; periodic DFT calculations indicate that the observed Raman behavior is consistent with empty D4R units containing one or two Si vacancies surrounded by Q 3 Si—consistent also with solid-state nuclear magnetic resonance measurement. These defects appear to heal during further crystallization, leading to the formation of defect-free LTA zeolite crystals. Altogether, our results provide deeper understanding on the roles of F – in charge balancing and stabilizing intact D4R units during zeolite formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Yb:Lu 2 O 3 single-crystal fiber: spectroscopy, amplification, and lasing

For the first time, to our knowledge, a lutetium oxide (Lu 2 O 3 ) single-crystal fiber (SCF) laser is demonstrated. The laser heated pedestal growth (LHPG) technique was used to pull Yb-doped Lu 2 O 3 SCFs between 10 and 50 mm long and with diameters between 150 and 225 μm. Spectroscopic properties are first reported in detail, as the two-site nature of the host demands careful attention. Short 10 mm long, unclad fibers were used as amplifier media in a single pass copropagating configuration. Then, a 50 mm long 0.1%Yb:Lu 2 O 3 SCF with a 180 μm diameter was configured to lase by butt-coupling mirrors on the ends and pumping at 976 nm. Lasing occurred at the 1033 nm peak of Yb, and a maximum output of around 300 mW is reported. Finally, the results indicate there is no, at least obvious, fundamental reason that should deter future interest in Lu 2 O 3 as a SCF platform, which has been considered to have high potential for power scaling based on its beneficial intrinsic properties.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Perovskite-Sensitized Upconversion under Operando Conditions

Perovskite-sensitized upconversion (UC) has resulted in near-infrared-to-visible UC at solar-relevant fluxes. However, the successful implementation of UC devices into operating solar cells will result in exposure to similar environmental stressors as for the commercial photovoltaics (PVs), mainly elevated temperatures, and continuous irradiation. In this article, we investigated the effects of these two stressors, heat and light, on the triplet generation process at the perovskite/rubrene interface. Following exposure to both stressors, local discrepancies across the upconversion device were discovered. Here, the first region showed changes to the morphology, and no detectable upconverted emission was observed. Through the combination of optical microscopy and spectroscopy, crystallization of the organic semiconductor layer, degradation of dibenzotetraphenylperiflanthene, and concurrent degradation of the perovskite sensitizer were found. These effects culminate in a reduction in both triplet generation and triplet–triplet annihilation. In the second region, no changes to the morphology were present and visible UC emission was observed following exposure to both stressors. To probe the triplet sensitization process at elevated temperatures, transient absorption spectroscopy was performed. The presence of the excited spin-triplet state of rubrene at 60 °C highlighted successful triplet generation even at elevated temperatures. This work emphasizes the challenges and continued potential for the integration of perovskite-sensitized UC into commercial photovoltaic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Novel dual-reflection design applied for ITER core x-ray spectrometer

Here. a novel dual-reflection configuration is introduced for the International Tokamak Experimental Reactor (ITER) core x-ray spectrometer to fit the allocated space where it will be placed accompanied by moving the detectors backward to reduce the incident radiation dose. The highly oriented pyrolytic graphite, which has a mosaic structure of microscopic crystallites, is chosen for the front reflector motivated by higher x-ray throughput and stronger misalignment tolerance compared to the perfect crystal reflector. In the ITER core x-ray spectrometer, a combination of several reflector-deflected Lines of Sight (LOSs) and a direct LOS is proposed for the first time named X-Ray Crystal Spectroscopy Core (XRCS-Core). The system is optimized to observe lines from externally seeded xenon and the intrinsic tungsten impurity, meeting both port integration needs and measurement requirements. Its spectral performance is simulated using an analytical-raytracing mixed code——XRSA, showing good imaging quality with a spectral resolution higher than 8000. The XRCS-Core system is thought to be applicable in various ITER scenarios through the assessment taking into account the spectrometers’ specifications and the chosen lines’ emissivity in different plasma parameters.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Polarization splitting with cubic crystals evaluated with synchrotron radiation

X-ray polarization-splitting crystals separate incident x rays into two components with perpendicular polarization by Bragg reflections at 45° from paired sets of internal planes. Here, the polarization-splitting properties of a germanium crystal are verified using incompletely polarized synchrotron radiation. Further, cleaner data would have come from a beam with a higher degree of polarization, which is achievable with small changes in the experimental geometry.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Experimental inference of neutral and impurity transport in Alcator C-Mod using high-resolution x-ray and ultra-violet spectra

We present experimental inferences of cross-field impurity transport coefficients for AlcatorC-Mod plasmas without edge-localized modes, leveraging a novel forward model for the entire Ca Kα spectrum, including satellite lines within the spectral range, to compare to high-resolution x-ray imaging crystal spectroscopy (XICS). These measurements are complemented by extreme ultra-violet (EUV) spectroscopy that constrains transport closer to the edge. Using new atomic data sets for both XICS and EUV analysis has enabled consideration of line ratios across both spectral ranges and has increased the accuracy of inferred transport coefficients. Inclusion of charge exchange between edge thermal neutrals and impurities is shown to be extremely important in C-Mod pedestals. Atomic D neutral densities from experimental D Lyα measurements at the midplane are compared to SOLPS-ITER simulations, finding good agreement. Bayesian inferences of impurity transport coefficients are presented for L-, EDA H-, and I-mode discharges, making use of the Aurora package for forward modeling and combining our spectroscopic constraints. Experimentally inferred diffusion profiles are found to match turbulent transport models at midradius within uncertainties, using both quasilinear gyro-fluid TGLF SAT-1 and nonlinear ion-scale gyrokinetic CGYRO simulations. Furthermore, significant discrepancies in convection are observed in some cases, suggesting difficulties in predictions of flat or hollow impurity profiles.

neutrals↗
DOE OSTI2024

Dielectronic satellite emission from a solid-density Mg plasma: Relationship to models of ionization potential depression

Here, we report on experiments where solid-density Mg plasmas are created by heating with the focused output of the Linac Coherent Light Source x-ray free-electron laser. We study the K-shell emission from the helium- and lithium-like ions using Bragg crystal spectroscopy. Observation of the dielectronic satellites in lithium-like ions confirms that the M-shell electrons appear bound for these high charge states. An analysis of the intensity of these satellites indicates that when modeled with an atomic-kinetics code, the ionization potential depression model employed needs to produce depressions for these ions which lie between those predicted by the well known Stewart-Pyatt and Ecker-Kroll models. These results are largely consistent with recent density functional theory calculations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Fe 3+ /Fe T ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy

The Fe 3+ /Fe T ratios (Fe 3+ /[Fe 2+ +Fe 3+ ]) in minerals can be used to understand their crystallization and post-crystallization conditions. However, as natural minerals are often zoned and contain inclusions, bulk techniques, e.g., wet chemistry, may not provide accurate Fe 3+ /Fe T values for a single phase of interest. We determined Fe 3+ /Fe T ratios of amphiboles in different crystallographic orientations by single-crystal synchrotron Mössbauer spectroscopy (SMS) in energy and time domain modes from four volcanic localities (Long Valley Caldera, Mount St. Helens, Lassen Volcanic Center, U.S.A., and Mt. Pinatubo, Philippines). The high spatial resolution (as low as 12 × 12 μm spot size) and standard-free nature of SMS allow the detection of intra-grain compositional heterogeneities in Fe 3+ /Fe T with relatively low uncertainties. Here, we combine SMS with major element compositions, water contents, and hydrogen isotope compositions to document the Fe 3+ /Fe T ratios as a function of mineral composition and post-crystallization dehydrogenation. Spectra were fitted with up to five distinct sites: ferrous iron on M(1), M(2), M(3), and ferric iron on M(2) and M(3), consistent with X-ray diffraction studies on single crystals of amphibole. The Fe 3+ /Fe T ratios range from 0.14 ± 0.03 (Long Valley Caldera), 0.51 to 0.63 ± 0.02 (representing intra-grain heterogeneities, Mount St. Helens) to 0.86 ± 0.03 (Lassen Volcanic Center). The latter grain experienced post-crystallization dehydrogenation, shown by its low water content (0.6 ± 0.05 wt%) and its elevated hydrogen isotope composition (δD = +25 ± 3‰ relative to SMOW). The Fe 3+ /Fe T ratios of 0.62 ± 0.01 and 0.20 ± 0.01 of two Mt. Pinatubo grains correlate with high-Al 2 O 3 cores and low-Al 2 O 3 rims and smaller phenocrysts in the sample, respectively. This study shows that SMS is capable of distinguishing two different domains with dissimilar Fe 3+ /Fe T values formed under different crystallization conditions, demonstrating that SMS in combination with major element, water, and hydrogen isotope compositions allows the interpretation of amphibole Fe 3+ /Fe T ratios in the context of crystallization and post-crystallization processes.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Remote sensing of Pu in uranyl nitrate crystals using reflectance spectroscopy and chemometrics

Remote quantification of Pu(VI) (0–5 mol%) co-crystallized with U in uranyl nitrate hexahydrate (UNH) crystals was achieved in a glove box using reflectance spectroscopy coupled with chemometric modeling. Reflectance spectra were also acquired for Pu(IV) and Np(VI) (0–5 mol%) crystallized with UNH; revealing spectral features consistent with their solution-phase analogs. Principal component analysis revealed Pu(IV/VI) and Np(VI) concentrations as the primary source of variation in the data, informing the development of a supervised partial least squares regression model for Pu(VI). The resulting calibration demonstrated robust performance, with replicate root mean square errors near 10% and quantifiable limits near 0.2 mol% Pu(VI) relative to U. The Pu(VI) remained stable in the crystalline UNH matrix for at least one week with minimal reduction to Pu(IV). Notably, Pu(VI) and Np(VI) incorporation in UNH quenched U(VI) fluorescence while Pu(IV) did not. This study presents a noninvasive, spectroscopic approach for solid-state Pu quantification, with direct implications for material accountability and nuclear nonproliferation monitoring.

Sadergaski, Luke R. [Oak Ridge National Laboratory↗
DOE OSTI2024

Identification and Suppression of Point Defects in Bromide Perovskite Single Crystals Enabling Gamma‐Ray Spectroscopy

Abstract Methylammonium lead tribromide (MAPbBr 3 ) stands out as the most easily grown wide‐band‐gap metal halide perovskite. It is a promising semiconductor for room‐temperature gamma‐ray ( γ ‐ray) spectroscopic detectors, but no operational devices are realized. This can be largely attributed to a lack of understanding of point defects and their influence on detector performance. Here, through a combination of crystal growth design and defect characterization, including positron annihilation and impedance spectroscopy, the presence of specific point defects are identified and correlated to detector performance. Methylammonium (MA) vacancies, MA interstitials, and Pb vacancies are identified as the dominant charge‐trapping defects in MAPbBr 3 crystals, while Br vacancies caused doping. The addition of excess MABr reduces the MA and Br defects and so enables the detection of energy‐resolved γ ‐ray spectra using a MAPbBr 3 single‐crystal device. Interestingly, the addition of formamidinium (FA) cations, which converted to methylformamidinium (MFA) cations by reaction with MA + during crystal growth further reduced MA defects. This enabled an energy resolution of 3.9% for the 662 keV 137 Cs line using a low bias of 100 V. The work provides direction toward enabling further improvements in wide‐bandgap perovskite‐based device performance by reducing detrimental defects.

Ni, Zhenyi↗
DOE OSTI2022

Inferring relative dose-dependent color center populations in proton irradiated thoria single crystals using optical spectroscopy

In this work, we have utilized photoluminescence spectroscopy and optical ellipsometry to characterize the dose-dependence of the photoluminescence emission intensity and changes in optical absorption of thoria single crystals subject to irradiation with energetic protons at room- and elevated-temperatures. The photoluminescence peaks and the optical absorption bands are attributed to creation of new electronic states emerging from defects resulting from displacement damage. These bands are most likely associated with electrons trapped at the oxygen vacancy sites similar to color centers formed in other irradiated oxides and halides. Our experimental observations are supported by a standard density functional theory calculation of the electronic structure in pristine and oxygen vacancy-bearing thoria crystals. The dose-dependence of the intensity of the photoluminescence peaks is used to parameterize a rate theory model that estimates the concentration of color centers in the irradiated crystals. This parameterization provides optimized migration barrier parameters for oxygen interstitials and vacancies that simultaneously capture the optical response of the crystals irradiated at room- and elevated-temperature. These optical spectroscopy techniques offer a promising pathway to characterize the population of color centers formed at the sites of oxygen anion vacancies, particularly in irradiated nuclear fuels, where atomic-level defects cannot be readily imaged using electron microscopy. When combined with other direct and indirect characterization tools, our approach can provide new insight into defect formation and accumulation in energy materials over single atomic to extended length scales.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Pressure-Induced Stabilization of Terbium(IV) in CsTb(CrO 4 ) 2 Characterized by X-ray Absorption Spectroscopy

Single crystals of CsTb(CrO 4 ) 2 and CsDy(CrO 4 ) 2 , where the lanthanide metals are in the trivalent state under ambient conditions, have been investigated under high-pressure conditions on the gigapascal scale utilizing a diamond anvil cell. These compounds were characterized by single-crystal X-ray diffraction in addition to high-pressure solid-state UV-vis-NIR spectroscopy, Raman spectroscopy, and Tb L 3 -edge highenergy- resolution fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES). The high-pressure UV-vis-NIR spectra reveal strong broadening of the metal-to-ligand charge transfer band to lower energies, associated with a visible color change from yellow to dark red/black. Clear evidence for the stabilization of Tb 4+ under high pressure is provided by the appearance of a second edge feature characteristic of Tb 4+ , starting at 19.62 GPa in the high-pressure L 3 -edge HERFD-XANES at around 7528 eV. This represents the first example of Tb 4+ being stabilized by high pressure and expands upon the limited chemistry of terbium in the tetravalent state.

Anions↗
DOE OSTI2022

Anti-electrostatic hydrogen-bonded tellurate dimers captured and stabilized by crystallization of a bis-iminoguanidinium salt

Anionic Te 2 O 6 (OH) 4 4– dimers have been captured by crystallization of a hydrated salt of glyoxal-bis-iminoguanidinium (GBIG), and structurally characterized by single-crystal X-ray diffraction and vibrational spectroscopy. The crystal structure reveals anti-electrostatic hydrogen-bonded chains of Te 2 O 6 (OH) 4 4– dimers, consisting of edge-sharing TeO 6 octahedra, stabilized by hydrogen bonding from the GBIG cations and the water molecules included in the crystal. FTIR spectroscopy confirms the presence of TeO 6 octahedra with characteristic Te–O stretching modes at 755 cm -1 and 689 cm -1 , while the observed stretching mode at 3459 cm-1 confirms the presence of axially-bonded hydroxyl groups. Raman spectroscopy and DFT calculations confirm the presence of the Te 2 O 6 (OH) 4 4– dimers in the crystalline phase and of the TeO(OH) 5 – monomers in solution.

36 MATERIALS SCIENCE↗
DOE OSTI2022

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. Here, 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗