Vacuum Ultraviolet Spectroscopy Research Articles

Investigating the effect of BT direction on W source-to-core pathways during the SAS-VW campaign on DIII-D

Experiments using the V-shaped closed slot tungsten (W) coated SAS-VW divertor in DIII-D studied the effects of the BT direction on core contamination of eroded tungsten from a closed slot divertor configuration. Core W content is inferred using soft-X ray tomography (SXR) and vacuum ultraviolet spectroscopy (SPRED), while W divertor erosion is inferred from visible spectroscopy of W emission (400.9 nm) measured by in-slot filterscopes (filtered photo-multipliers). Post-mortem analysis from the campaign discovered tile misalignment leading to suspected pronounced leading-edge erosion in the unfavorable BT direction (ion B→×∇B→ drift away from divertor) likely not captured by diagnostics. However, empirical findings show up to ∼ 2-3x larger core contamination in the favorable BT direction even considering no additional W erosion from leading edges. A “source-to-core efficiency factor” is derived to estimate the effects of leading-edge erosion and compare W contamination for two pairs of H-mode discharges in opposite BT directions. While having differing absolute parameters, similar core impurity density gradients suggest comparable core impurity transport. These results show that favorable BT may have stronger source-to-core pathways for W impurities sourced from the outer divertor region. Possible explanations could include the effects of E→×B→ drifts on W transport in the scrape-off-layer (SOL) as well as previously determined fast SOL inner target directed flows in favorable BT.

LUMINESCENCE CHARACTERISTICS OF CASO4:TB,M (M=NA,K,RB) PHOSPHORS

In the present study, the investigation of complex luminescence terbium centres as well as the analysis of technological features of the synthesis of small-grained wide-gap CaSO :Tb3+ anhydrite phosphors containing 1% of Tb3+ and some amount of additional impurity ions (Na+, K+, Rb+) have been continued using the methods of optical and thermoactivation spectroscopy. Of particular interest was a contribution of calcium ions into formation of complex luminescence centres. Ca causes efficient dynamic hybridization of electronic states and influence on the formation of terbium and near-terbium electronic excitations. The excitation spectra of Tb3+-centre emission have been measured in the VUV spectral range at 77 or 300 K. The excitation band related to the lowest f–d transition of Tb3+ ions at ≈5.9 eV in CaSO4 undergoes broadening toward the long- wavelength side, when the radius of a charge compensator increases (K+→ Rb+). The band at 7.5–9 eV ascribed to the excitation of oxyanions has a different shape in CaSO4:Tb,K and CaSO4:Tb,Rb. Thermally stimulated luminescence (80–700 K) have been analyzed for a set of anhydrite phosphors previously irradiated by X-rays at 80 and 300 K. Keywords: CaSO , Tb3+, photoluminescence, thermoluminescence, vacuum ultraviolet spectroscopy.

Design of a multichannel vacuum ultraviolet spectroscopy system for SPARC.

The design of a vacuum ultraviolet spectroscopy system has been performed to monitor and provide feedback for impurity control in SPARC. The spectrometer, covering a wavelength range of 10-2000Å through a flat-field configuration with diffraction gratings, incorporates five survey lines of sight. This allows for comprehensive impurity analysis across the core and four divertor regions (inner/outer and upper/lower). Its compact modular design facilitates vertical stacking of each spectrometer unit, significantly reducing space in the tokamak hall, where a dedicated radiation shielding bunker will be built. Safety features include a secondary helium enclosure to mitigate tritium permeation risks during deuterium-tritium (D-T) operations and shielding within the beamlines for enhanced radiation protection. The silicon carbide mirror design for divertor observation ensures its survivability in the in-vessel environment of SPARC, validated by thermal and electromagnetic analysis. Signal modeling and data acquisition testing results show that an exposure time of a few milliseconds is appropriate considering photon flux reaching the detector, demonstrating the system's capability for discharge control that includes disruption avoidance.

Wavelength calibration and spectral analysis of vacuum ultraviolet spectroscopy in EAST

A vacuum ultraviolet (VUV) spectroscopy with a focal length of 1 m has been engineered specifically for observing edge impurity emissions in Experimental Advanced Superconducting Tokamak (EAST). In this study, wavelength calibration for the VUV spectroscopy is achieved utilizing a zinc lamp. The grating angle and charge-coupled device (CCD) position are carefully calibrated for different wavelength positions. The wavelength calibration of the VUV spectroscopy is crucial for improving the accuracy of impurity spectral data, and is required to identify more impurity spectral lines for impurity transport research. Impurity spectra of EAST plasmas have also been obtained in the wavelength range of 50–300 nm with relatively high spectral resolution. It is found that the impurity emissions in the edge region are still dominated by low-Z impurities, such as carbon, oxygen, and nitrogen, albeit with the application of full-tungsten divertors on the EAST tokamak.

Ion temperature and rotation velocity measurements of carbon and boron ions using VUV spectroscopy on EAST.

A space-resolved vacuum ultraviolet spectroscopy is employed to measure impurity emission profiles (500-3200Å) on EAST. This study successfully captures C IV (1548.20 and 1550.77Å) lines emitted from carbon ions and derives ion temperatures using Doppler broadening and a collision model based on their intensity ratios. Both the emission intensity and ion temperature profiles are determined. However, the calculated results reveal a lower temperature of around 10-20eV with the collision model, suggesting a potential need for further correction in subsequent calculations. Furthermore, this study explores relative rotation velocities from the Doppler shift, indicating an increase in toroidal rotation velocity with applied neutral beam injection. The measured results exhibit concordance with the charge exchange recombination spectrometer data. Furthermore, during boron powder dropping discharges on EAST, B II (1623.60, 1623.79, 1623.95, 1624.02, 1624.17, and 1624.38Å) emission lines exhibiting a similar time behavior trend with boron powder injection are identified. Ion temperatures are measured using B II (1362.46Å) through the Doppler broadening method. These techniques hold significant promise for future impurity analysis at the edge of EAST, providing valuable insights into the behavior of carbon and boron ions.

Luminescence and Electron–Hole-Trapping Centers in α-Ca2P2O7−Mn

The mechanisms of formation of induced intrinsic and impurity radiative states, which consist of intrinsic and impurity electron–hole-trapping center states in irradiated Ca2P2O7−Mn and Ca2P2O7 phosphates, were investigated using thermoactivation and vacuum-ultraviolet spectroscopy methods. These centers are excited at photon energies of 4.0 eV and 4.5 eV, which are within the matrix’s transparency region. New radiative-induced states at 3.06 eV and 2.92 eV are demonstrated to be generated upon the excitation of anions by photons with energies of 5.0 and 5.64 eV. This process is due to charge transfer from the ion to the impurities, specifically Mn2+(O2−−Mn2+) and the neighboring ion O 2−−(P2O7)4−. Furthermore, upon the excitation of matrix anions with photon energies exceeding the band gap (8.0–8.25 eV), electron-trapping by impurities such as Mn2+ and (P2O7)4− ions results.

Method development and evaluation of product gas mixture from a semi-industrial scale fluidized bed steam cracker with GC-VUV

Steam cracking in fluidized beds offers an alternative to conventional steam cracking for sustainable hydrocarbon production. This approach has gained interest, particularly in the context of recycling plastics to generate valuable hydrocarbons. Integrating this process into existing petrochemical clusters necessitates a thorough characterization of the products derived from this new feedstock. This work focuses on addressing the challenges associated with species quantification and characterization time for assessing the product mixture resulting from a steam cracking process. The experiments were conducted in a semi-industrial scale dual fluidized bed steam cracker, utilizing polyethylene as the feedstock. To sample species spanning from C1 to C18, cooling, scrubbing, and adsorption were introduced. These steps were integrated with GC-VUV (Gas Chromatography with Vacuum Ultraviolet Spectroscopy) and other widely recognized analytical methods to quantify the sampled species. The primary focus was on GC-VUV analysis as a suitable characterization method for identifying and quantifying C4 to C18 species, which can constitute up to 35% of the product mixture obtained from polyethylene steam cracking (750 °C to 850 °C). Quantifying C6 to C18 hydrocarbons becomes the time-critical step, with GC-VUV potentially achieving this in 1/6th of the analysis time and with relatively optimal quantification compared to the traditional characterization methods.

Quantitation of olefins in sustainable aviation fuel intermediates using principal component analysis coupled with vacuum ultraviolet spectroscopy

Olefins, a common intermediate from biomass conversion processes, are undesirable in jet fuel because of their poor thermal stability. This paper presents an approach for olefin quantitation using 2D gas chromatography coupled with vacuum ultraviolet spectroscopy. Principal component analysis was used to reduce the dimensionality of the spectroscopic data from a highly olefinic fuel intermediate. A principal component template was created that enabled olefin quantitation, which was compared to the existing GCxGC-VUV approach from the literature. The principal component method was able to identify and quantify trace amounts of cyclodienes, which were present at only 0.01 wt% in the fuel sample. The principal component approach also identifies species that fall outside of the GCxGC template. For instance, quantitation with the literature method resulted in an olefin concentration of 0.95 times that of the principal component method due to olefins falling outside of the expected GCxGC regions. The principal component results were compared with 13C and 1H NMR data, which confirmed that the fuel had a high concentration of olefins and alkanes with little aromatic content.

Energy Transfer in the CaSO4−Dy Thermoluminescent Dosimeter from the Excited State of the SO42− Anionic Complex to the Impurities

The creation of a combined radiative state at 2.95–3.1 eV in the phosphor CaSO4−Dy 3+ has been investigated using vacuum ultraviolet and thermoactivation spectroscopy methods. It is shown that the combined radiative electronic state is formed from the radiative electronic states of the impurity electronic trapping centers Dy 2+− SO4− and the intrinsic electronic radiative states SO43−−SO4− during the excitation of the anion complex SO42−, as a result of charge transfer from the excited anion complex O 2−−Dy 3+ to the impurities and the neighboring anion complex O2−− SO42−. In the CaSO4−Dy phosphor, the combined radiative electronic state and impurity emission of Dy 3+, 2.16 eV and 2.56 eV are excited by photons with energies of 3.95–4.0 eV and 4.5–4.6 eV. Energy transfer from the matrix to the Dy 3+ impurities is revealed upon thermal exposure as a result of the ionization of the electronic capture centers of Dy2+ and SO43−.

Molecular Spectroscopy: Underutilized Detection for Gas Chromatography

Molecular spectroscopy techniques, most commonly ultraviolet-visible (UV-vis), are usually thought of as analyzing liquid-phase samples, with techniques such as high-performance liquid chromatography (HPLC). Although not as common as in HPLC, molecular spectroscopy can be used with gas chromatography (GC) as well. In this installment, we examine molecular spectroscopy in combination with GC. The two most common techniques used with GC today are Fourier transform infrared spectrometry (FT-IR) and vacuum ultraviolet spectroscopy (VUV). Both provide structural and quantitative information and can be used in complementary fashion with the more common GC–mass spectrometry (GC–MS) and classical detectors. We will discuss the basics of GC–FT-IR and GC–VUV, when and when not to use them, and how they compare to and complement classical detectors.

Unraveling the Conformational Preference of Morpholine: Insights from Infrared Resonant Vacuum Ultraviolet Photoionization Mass Spectroscopy.

The preference for different conformations in morpholine has a notable effect on its behavior and reactivity in organic synthesis. Herein, we explored the intricate conformational properties of morpholines through a combination of advanced mass spectrometric techniques and theoretical calculations. Notably, we employed infrared (IR) resonant vacuum ultraviolet (VUV) mass-analyzed threshold ionization spectroscopy to measure the unique vibrational spectra of the distinct conformers (Chair-Eq and Chair-Ax) in morpholine for the first time. Through precise VUV photon energy adjustments to coincide with the vibrational excitation via IR absorption, we effectively pinpointed the adiabatic ionization thresholds corresponding to the Chair-Eq (65 442 ± 4 cm-1) and Chair-Ax (65 333 ± 4 cm-1) conformers. This allowed us to accurately determine the conformational stability between the two conformers (109 ± 4 cm-1). By shedding light on the conformational properties of morpholine, this study brings far-reaching implications to the fields of organic synthesis and pharmaceutical research.

Methyl radical chemistry in non-oxidative methane activation over metal single sites

Molybdenum supported on zeolites has been extensively studied as a catalyst for methane dehydroaromatization. Despite significant progress, the actual intermediates and particularly the first C-C bond formation have not yet been elucidated. Herein we report evolution of methyl radicals during non-oxidative methane activation over molybdenum single sites, which leads selectively to value-added chemicals. Operando X-ray absorption spectroscopy and online synchrotron vacuum ultraviolet photoionization mass spectroscopy in combination with electron microscopy and density functional theory calculations reveal the essential role of molybdenum single sites in the generation of methyl radicals and that the formation rate of methyl radicals is linearly correlated with the number of molybdenum single sites. Methyl radicals transform to ethane in the gas phase, which readily dehydrogenates to ethylene in the absence of zeolites. This is essentially similar to the reaction pathway over the previously reported SiO2 lattice-confined single site iron catalyst. However, the availability of a zeolite, either in a physical mixture or as a support, directs the subsequent reaction pathway towards aromatization within the zeolite confined pores, resulting in benzene as the dominant hydrocarbon product. The findings reveal that methyl radical chemistry could be a general feature for metal single site catalysis regardless of the support (either zeolites MCM-22 and ZSM-5 or SiO2) whereas the reaction over aggregated molybdenum carbide nanoparticles likely facilitates carbon deposition through surface C-C coupling. These findings allow furthering the fundamental insights into non-oxidative methane conversion to value-added chemicals.

Learning to predict sustainable aviation fuel properties: A deep uncertainty quantification viewpoint

Machine/deep learning (DL) predictions of sustainable aviation fuel’s (SAF) physiochemical properties from chemical data offers a rapid way to prescreen the potential viability of new SAF candidates but is limited by uncertainties. In this article, the uncertainties arising from insufficient training data (epistemic) and finite-resolution chemical features (heteroscedastic) are addressed by conducting a deep uncertainty quantification (UQ) study using a Bayesian neural network ensemble (BNNE) to model and analyze such uncertainties. In particular, flash point is predicted from two-dimensional gas chromatography (GC×GC) features in various scenarios where differences in epistemicity and heteroscedasticity exist. Several insights are obtained: (1) Overparameterization of the network provides buffer against epistemicity and should be advocated in the absence of sufficient data. (2) Reducing the epistemic uncertainty via GC×GC localization does not always improve accuracy, highlighting the necessity of a probabilistic formulation to prevent overconfident but erroneous predictions. (3) Heteroscedastic uncertainty is larger and irreducible for lower resolution features, e.g., GC separated by chemical family but not molecular formulae. These findings aim not only to facilitate trustworthy DL practices in SAF modeling but also to emphasize the importance of establishing a big data pipeline and the design of finer features (e.g., isomer differentiation via vacuum ultraviolet spectroscopy) to mitigate these uncertainties.

Gas chromatography-vacuum ultraviolet spectroscopy in petroleum and fuel analysis.

In the modern world, energy and fuels are of utmost importance. Rapid characterization of petroleum and other hydrocarbon-based fuel is a well-researched field. Gas chromatography has traditionally been used to separate the different species and characterize the chemical content in fuels. Ideally, every molecule would be separated and characterized, but due to the complexity of the petroleum matrix, many compounds coelute. With the help of different detectors, more information can be gained, but there does not exist a single detector that can unambiguously differentiate and identify every compound. Vacuum ultraviolet spectroscopy (VUV) is a relatively new detector that can alleviate many limitations of other detectors. Based on spectroscopic absorption, VUV detection can provide qualitative and quantitative information regarding the composition of different fuels. It also provides certain advantages, allowing the deconvolution of coeluting peaks and differentiation between constitutional isomers. VUV has been used to classify the range of chemical components in many diverse fuel samples. Here, the contributions of VUV detection to petrochemical analysis to date are reviewed.

A setup for vacuum-ultraviolet spectroscopy of the 229Th low-energy isomer

The ground-state transition of the low-energy isomer in 229Th has been proposed as the basis for the development of a novel optical clock as a tool for fundamental-physics studies. Vacuum-ultraviolet studies of the β-decay of 229Ac recently enabled to measure the de-excitation energy of the isomer with a seven-fold improvement in precision compared to previous results by directly observing photons from the isomer’s radiative decay. In this contribution, the setup used for this study and the systematic uncertainty on the measured photon wavelength is discussed.

Limits of identification using VUV spectroscopy applied to C8H18 isomers isolated by GC×GC.

The vacuum ultraviolet detector for gas chromatography can be used to identify structural differences between isomers with similar chromatographic elution times, which adds detail to characterization, valuable for prescreening of sustainable aviation fuel candidates. Although this capability has been introduced elsewhere, vacuum ultraviolet spectroscopy for saturated hydrocarbons has been examined minimally, as the similarities between their spectra are much less significant than their aromatic counterparts. The fidelity with which structural differences can be identified has been unclear. In this work, all possible structural isomers of C8H18 are measured and determined to have unambiguously unique vacuum ultraviolet spectra. Using a statistically based residual comparison approach, the concentration limits at which the spectral differences are interpretable are tested in both a controlled study and a real fuel application. The concentration limit at which the spectral differences between C8H18 isomers are unambiguous is below 0.40% by mass and less than 0.20% with human discretion in our experimental configuration.

Temperature-dependent vacuum ultraviolet photoluminescence spectroscopy of transition metal and rare earth co-doped ZnO phosphors: a synchrotron-based investigation

Temperature-dependent vacuum ultraviolet photoluminescence spectroscopy of transition metal and rare earth co-doped ZnO phosphors: a synchrotron-based investigation

Advanced method for efficient functionalization of polymers by intermediate free-radical formation with vacuum-ultraviolet radiation and producing superhydrophilic surfaces

An efficient approach for tailoring surface properties of polymers is presented, which enables rapid modification leading to superhydrophilic properties. The approach is based on vacuum-ultraviolet radiation (VUV) pretreatment of the surface to create reactive dangling bonds. This step is followed by a second treatment using neutral oxygen atoms that react with the dangling bonds and form functional groups. The beneficial effect of VUV pretreatment for enhanced functionalization was clearly demonstrated by comparing VUV pretreatment in plasmas created in different gases, i.e., hydrogen, nitrogen, and oxygen, which differ in the intensity of VUV/UV radiation. The emission intensity of VUV radiation for all gases was measured by vacuum ultraviolet spectroscopy. It was shown that VUV has a strong influence on the treatment time and final surface wettability. A superhydrophilic surface was obtained only if using VUV pretreatment. Furthermore, the treatment time was significantly reduced to only a second of treatment. These findings show that such an approach may be used to enhance the surface reaction efficiency for further grafting of chemical groups.

Observation of the radiative decay of the 229Th nuclear clock isomer.

The radionuclide thorium-229 features an isomer with an exceptionally low excitation energy that enables direct laser manipulation of nuclear states. It constitutes one of the leading candidates for use in next-generation optical clocks1-3. This nuclear clock will be a unique tool for precise tests of fundamental physics4-9. Whereas indirect experimental evidence for the existence of such an extraordinary nuclear state is substantially older10, the proof of existence has been delivered only recently by observing the isomer's electron conversion decay11. The isomer's excitation energy, nuclear spin and electromagnetic moments, the electron conversion lifetime and a refined energy of the isomer have been measured12-16. In spite of recent progress, the isomer's radiative decay, a key ingredient for the development of a nuclear clock, remained unobserved. Here, we report the detection of the radiative decay of this low-energy isomer in thorium-229 (229mTh). By performing vacuum-ultraviolet spectroscopy of 229mTh incorporated into large-bandgap CaF2 and MgF2 crystals at the ISOLDE facility at CERN, photons of 8.338(24) eV are measured, in agreement with recent measurements14-16 and the uncertainty is decreased by a factor of seven. The half-life of 229mTh embedded in MgF2 is determined to be 670(102) s. The observation of the radiative decay in a large-bandgap crystal has important consequences for the design of a future nuclear clock and the improved uncertainty of the energy eases the search for direct laser excitation of the atomic nucleus.

Structures of (Pyrazine)2 and (Pyrazine)(Benzene) Dimers Investigated with Infrared-Vacuum Ultraviolet Spectroscopy and Quantum-Chemical Calculations: Competition among π-π, CH···π, and CH···N Interactions.

The structures of a pyrazine dimer (pyrazine)2 and (pyrazine)(benzene) hetero-dimer cooled in a supersonic beam were investigated by the measurement of the infrared spectra in the C-H stretching region with infrared-vacuum ultraviolet (IR-VUV) spectroscopy and quantum-chemical calculations. The stabilization energy calculation at the CCSD(T)/aug-cc-pVTZ level of theory predicted three isomers for (pyrazine)2 and three for (pyrazine)(benzene) with energy within 6 kJ/mol. Among them, the cross-displaced π-π stacked structure is the most stable in both dimers. In the observed IR spectra, both dimers exhibited two intense bands near 3065 cm-1, with intervals of 8 cm-1 in (pyrazine)2 and 11 cm-1 in (pyrazine)(benzene), while only one band appeared in the monomer. For (pyrazine)(benzene), we also measured the IR spectrum of (pyrazine)(benzene-d6), where the interval of the two bands was unchanged. The analysis of the observed IR spectra with anharmonic calculations suggested the coexistence of three isomers of (pyrazine)2 and (pyrazine)(benzene) in a supersonic jet. For (pyrazine)2, the two isomers which were previously assigned to the H-bonded planar and the π-π stacked structures respectively were reassigned to the cross-displaced π-π stacked and T-shaped structures, respectively. In addition, the quantum chemical calculation and IR-VUV spectral measurement suggested the coexistence of the H-bonded planar isomer in the jet. For (pyrazine)(benzene), the IR spectrum of the (pyrazine) site showed a similar spectral pattern to that of (pyrazine)2, especially the split at ∼3065 cm-1. However, the anharmonic analysis suggested that they are assigned to the different vibrational motions of (pyrazine). The anharmonic vibrational analysis is essential to associate the observed IR spectra with the correct structures of the dimer.