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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Dynamic computational optical fringe mitigation in tunable laser absorption spectroscopy

In optical spectroscopic systems where unwanted optical scattering cannot be eliminated, Fabry-Pérot etalons cause unpredictable changes in the spectral background. Frequent system calibration is then required to maintain the desired measurement accuracy, which presents a major limitation to the spectrometer. We introduce a computational approach to mitigate the adverse effects of optical fringing without hardware modifications. Motivated by experimental observations of complicated fringe behaviors, we simplify the problem by decomposing the fringe background into component etalons that can be addressed according to their individual characteristics. The effectiveness of the proposed method is demonstrated on a silicon photonic methane sensor, where accurate measurements of methane concentration are obtained from spectral data strongly affected by optical fringes.

Teng, Chu C. (ORCID:0000000152744835)↗
DOE OSTI2022

Beyond green with synthetic chlorophylls – Connecting structural features with spectral properties

The distinct features of chlorophylls in photosynthesis have led to the formation of numerous derivatives for applications encompassing solar energy conversion, molecular photonics, photodynamic therapy, and molecular imaging. Synthetic chlorins created de novo and bearing a geminal dimethyl group in the reduced ring have proved invaluable for fundamental studies. Four decades of research have led to accumulation of tabulated spectra for > 400 such synthetic chlorins with distinct structural frameworks (17-oxochlorins, 13 1 -oxophorbines, chlorinimides) and substituents (alkyl, aryl, ethynyl, phenylethynyl, acetyl, formyl) located at specific (meso, β) positions. In this review, spectral traces (324 absorption, 247 fluorescence) are assembled along with photophysical data including the molar absorption coefficient (ε), fluorescence quantum yield (Φ f ) and singlet excited-state lifetime (τ s ). The review uses the accumulated spectral data derived from chlorins all containing a uniform molecular scaffold to (1) highlight the effects of molecular structure on spectral features, and (2) identify trends including how ε, Φ f and τ s vary with wavelength and other features. Use of a common geminal-dimethyl-substituted chlorin scaffold – beginning with no substituents, to one substituent at designated sites, and to 2 or more substituents – provides a systematic Aufbau approach for understanding the absorption spectra of chlorins on a path to and beyond the native chlorophylls. Finally, the review provides insights concerning the rational design of potent analogues of Nature’s preeminent red-region absorbers for potential utilization in diverse applications and is aimed at multiple audiences: those interested in spectral properties, tetrapyrrole photophysics, and the molecular design of new chromophores.

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

Dirhodium(II,II) Complexes as Panchromatic Single-Molecule Photocatalysts for Hydrogen Evolution

The growing global energy demand and climate change have prompted a shift from carbon-based fuels to sustainable energy sources. Hydrogen production by harnessing solar energy and using abundant proton sources represents an attractive approach to addressing this crisis. Single-molecule single-chromophore photocatalysts, capable of both absorbing the incident photon and catalyzing the chemical transformation, are able to circumvent energy losses present in multicomponent systems that require a photosensitizer and a catalyst, often employing additional redox relay molecules. Here, the series of complexes derived from cis-[Rh 2 (μ-DPhF) 2 (μ-bncn) 2 ] 2+ (1; DPhF = N,N′-diphenylformamidinate, bncn = benzo[c]cinnoline) discussed in this Account presents robust and air-stable single-molecule photocatalysts with panchromatic absorption from the ultraviolet spectral region to the near-infrared (NIR), with high turnover frequencies of ∼20 to 30 h –1 under red light irradiation. For comparison, other single-molecule hydrogen-evolving photocatalysts reported to date exhibit low photocatalytic efficiency, are not operable in the visible or NIR regions, and are unstable under an ambient atmosphere.

Absorption↗
DOE OSTI2022

Evidence of Morphological Change in Sulfur Cathodes upon Irradiation by Synchrotron X-rays

While the development of lithium–sulfur battery cathodes has benefited substantially from the use of in situ and ex situ X-ray absorption studies, the degree of undesired influence from synchrotron radiation has not been studied. In this study, we present evidence of severe beam damage on sulfur cathodes under irradiation by synchrotron X-rays. Specifically, X-ray fluorescence mapping with relatively low dosage was conducted to observe the morphological changes after conducting X-ray absorption spectroscopy (XAS). Under open-circuit conditions, the morphology of the sulfur spontaneously changes and tends to migrate out of the region of XAS sampling. Our work indicates that effort should be placed in first obtaining a no-change/stable open-circuit baseline when attempting to conduct in operando studies of lithium–sulfur batteries using synchrotron radiation with an energy of <7.7 keV and a flux of >6 × 10 12 photons s –1 .

25 ENERGY STORAGE↗
DOE OSTI2020

Uncovering the Role of Hole Traps in Promoting Hole Transfer from Multiexcitonic Quantum Dots to Molecular Acceptors

The understanding of electronic dynamics in multiexcitonic quantum dots (QDs) is important for designing efficient systems useful in high power scenarios, such as solar concentrators and multielectron charge transfer. The multiple charge carriers within a QD can undergo undesired Auger recombination events, which rapidly annihilate carriers on picosecond time scales and generate heat from absorbed photons instead of useful work. Compared to the transfer of multiple electrons, the transfer of multiple holes has proven to be more difficult due to slower hole transfer rates. To probe the competition between Auger recombination and hole transfer in CdSe, CdS, and CdSe/CdS QDs of varying sizes, we synthesized a phenothiazine derivative with optimized functionalities for binding to QDs as a hole accepting ligand and for spectroscopic observation of hole transfer. Transient absorption spectroscopy was used to monitor the photoinduced absorption features from both trapped holes and oxidized ligands under excitation fluences where the averaged initial number of excitons in a QD ranged from ~1 to 19. We observed fluence-dependent hole transfer kinetics that last around 100 ps longer than the predicted Auger recombination lifetimes, and the transfer of up to 3 holes per QD. Theoretical modeling of the kinetics suggests that binding of hole acceptors introduces trapping states significantly different from those in native QDs passivated with oleate ligands. Holes in these modified trap states have prolonged lifetimes, which promotes the hole transfer efficiency. These results highlight the beneficial role of hole-trapping states in devising hole transfer pathways in QD-based systems under multiexcitonic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Beyond integration: modeling every pixel to obtain better structure factors from stills

Most crystallographic data processing methods use pixel integration. In serial femtosecond crystallography (SFX), the intricate interaction between the reciprocal lattice point and the Ewald sphere is integrated out by averaging symmetrically equivalent observations recorded across a large number (10 4 -10 6 ) of exposures. Although sufficient for generating biological insights, this approach converges slowly, and using it to accurately measure anomalous differences has proved difficult. This report presents a novel approach for increasing the accuracy of structure factors obtained from SFX data. A physical model describing all observed pixels is defined to a degree of complexity such that it can decouple the various contributions to the pixel intensities. Model dependencies include lattice orientation, unit-cell dimensions, mosaic structure, incident photon spectra and structure factor amplitudes. Maximum likelihood estimation is used to optimize all model parameters. The application of prior knowledge that structure factor amplitudes are positive quantities is included in the form of a reparameterization. The method is tested using a synthesized SFX dataset of ytterbium(III) lysozyme, where each X-ray laser pulse energy is centered at 9034 eV. This energy is 100 eV above the Yb 3+ L -III absorption edge, so the anomalous difference signal is stable at 10 electrons despite the inherent energy jitter of each femtosecond X-ray laser pulse. This work demonstrates that this approach allows the determination of anomalous structure factors with very high accuracy while requiring an order-of-magnitude fewer shots than conventional integration-based methods would require to achieve similar results.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Asynchronous x-ray multiprobe data acquisition for x-ray transient absorption spectroscopy

Laser pump X-ray Transient Absorption (XTA) spectroscopy offers unique insights into photochemical and photophysical phenomena. X-ray Multiprobe data acquisition (XMP DAQ) is a technique that acquires XTA spectra at thousands of pump-probe time delays in a single measurement, producing highly self-consistent XTA spectral dynamics. In this work, we report two new XTA data acquisition techniques that leverage the high performance of XMP DAQ in combination with High Repetition Rate (HRR) laser excitation: HRR-XMP and Asynchronous X-ray Multiprobe (AXMP). HRR-XMP uses a laser repetition rate up to 200 times higher than previous implementations of XMP DAQ and proportionally increases the data collection efficiency at each time delay. This allows HRR-XMP to acquire more high-quality XTA data in less time. AXMP uses a frequency mismatch between the laser and x-ray pulses to acquire XTA data at a flexibly defined set of pump-probe time delays with a spacing down to a few picoseconds. AXMP introduces a novel pump-probe synchronization concept that acquires data in clusters of time delays. Further, the temporally inhomogeneous distribution of acquired data improves the attainable signal statistics at early times, making the AXMP synchronization concept useful for measuring sub-nanosecond dynamics with photon-starved techniques like XTA. In this paper, we demonstrate HRR-XMP and AXMP by measuring the laser-induced spectral dynamics of dilute aqueous solutions of Fe(CN) 6 4₋ and [Fe II (bpy) 3 ] 2+ (bpy: 2,2'-bipyridine), respectively.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Ultrafast Production of NiCO and Ni Following 197 nm Photodissociation of Nickel Tetracarbonyl

Herein, we report on the ultrafast photodissociation of nickel tetracarbonyl—a prototypical metal–ligand model system—at 197 nm. Using mid-infrared transient absorption spectroscopy to probe the bound C≡O stretching modes, we find evidence for the picosecond time scale production of highly vibronically excited nickel dicarbonyl and nickel monocarbonyl, in marked contrast with a prior investigation at 193 nm. Further spectral evolution with a 50 ps time constant suggests an additional dissociation step; the absence of any corresponding growth in signal strongly indicates the production of bare Ni, a heretofore unreported product from single-photon excitation of nickel tetracarbonyl. Thus, by probing the deep UV-induced photodynamics of a prototypical metal carbonyl, this Letter adds time-resolved spectroscopic signatures of these dynamics to the sparse literature at high excitation energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photoabsorption, photoionization, and Auger processes at the carbon K edge in C H 3 I

The dynamics of photoabsorption, photoionization, and the associated Auger decay have been investigated at the carbon K edge in methyl iodide (CH 3 I) using linearly polarized synchrotron radiation. Ion yield measurements were used to investigate transitions in the pre-edge region due to excitations into either unoccupied valence or Rydberg states. The assignment of these transitions was achieved through comparison with theoretical x-ray absorption spectra calculated using time-dependent density functional theory, within the Tamm-Dancoff approximation. Several of the Rydberg states belonging to series converging onto the C1s ionization limit exhibit significant vibrational structure that is also interpreted using theoretical calculations. The C1s in CH 3 I photoelectron spectrum was measured, and the observed vibrational structure was assigned with the aid of theoretical predictions. Polarization dependent, resonantly excited, valence shell photoelectron spectra were recorded at photon energies coinciding with the C1s → σ*, C1s → 6sa1 and C1s → 6pe transitions in CH 3 I , thereby allowing photoelectron angular distributions to be determined. The nonresonantly excited C(KVV) Auger electron spectrum was measured and some of the features observed at high kinetic energies were attributed to transitions into valence orbitals possessing significant iodine character. The contributions of participator and spectator Auger decay to the resonantly excited photoelectron spectra have been assessed. The influence of participator decay appears minor whereas spectator decay results in the enhanced population of satellite states.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Increased phase precision of spatial light modulators using irrational slopes: application to attosecond metrology

The ability of spatial light modulators (SLMs) to modify the amplitude and phase of light has proved them invaluable to the optics and photonics community. In many applications, the bit-depth of SLMs is a major limiting factor dictated by a digital processor. As a result, there is usually a compromise between refresh speed and bit-depth. Here, we present a method to increase the effective bit-depth of SLMs, which utilizes a linear slope, as is commonly applied to deal with the zeroth-order effect. This technique was tested using two interferometric transient absorption spectroscopy setups. Through the high harmonic generation in gases producing a train of attosecond pulses and harmonics from solids in the ultraviolet, two pulses are generated that interfere in the far field providing a measurement of the optical phase. An increase in the precision far beyond the limit dictated by the digital processor in the bit-depth was found.

Harrison, Geoffrey R. (ORCID:0000000152141866)↗
DOE OSTI2022

Limits on X-Ray Polarization at the Core of Centaurus A as Observed with the Imaging X-Ray Polarimetry Explorer

We present measurements of the polarization of X-rays in the 2–8 keV band from the nucleus of the radio galaxy Centaurus A (Cen A), using a 100 ks observation from the Imaging X-ray Polarimetry Explorer (IXPE). Nearly simultaneous observations of Cen A were also taken with the Swift, NuSTAR, and INTEGRAL observatories. No statistically significant degree of polarization is detected with IXPE. These observations have a minimum detectable polarization at 99% confidence (MDP 99 ) of 6.5% using a weighted, spectral model-independent calculation in the 2–8 keV band. The polarization angle ψ is consequently unconstrained. Spectral fitting across three orders of magnitude in X-ray energy (0.3–400 keV) demonstrates that the SED of Cen A is well described by a simple power law with moderate intrinsic absorption (N H ~ 10 23 cm -2 ) and a Fe Kα emission line, although a second unabsorbed power law is required to account for the observed spectrum at energies below 2 keV. This spectrum suggests that the reprocessing material responsible for this emission line is optically thin and distant from the central black hole. Our upper limits on the X-ray polarization are consistent with the predictions of Compton scattering, although the specific seed photon population responsible for the production of the X-rays cannot be identified. The low polarization degree, variability in the core emission, and the relative lack of variability in the Fe Kα emission line support a picture where electrons are accelerated in a region of highly disordered magnetic fields surrounding the innermost jet.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

M-Edge Spectroscopy of Transition Metals: Principles, Advances, and Applications

M-edge X-ray absorption spectroscopy (XAS), which probes 3p→3d transitions in first-row transition metals, provides detailed insights into oxidation states, spin-states, and local electronic structure with high element and orbital specificity. Operating in the extreme ultraviolet (XUV) region, this technique provides sharp multiplet-resolved features with high sensitivity to ligand field and covalency effects. Compared to K- and L-edge XAS, M-edge spectra exhibit significantly narrower full widths at half maximum (typically 0.3–0.5 eV versus >1 eV at the L-edge and >1.5–2 eV at the K-edge), owing to longer 3p core-hole lifetimes. M-edge measurements are also more surface-sensitive due to the lower photon energy range, making them particularly well-suited for probing thin films, interfaces, and surface-bound species. The advent of tabletop high-harmonic generation (HHG) sources has enabled femtosecond time-resolved M-edge measurements, allowing direct observation of ultrafast photoinduced processes such as charge transfer and spin crossover dynamics. This review presents an overview of the fundamental principles, experimental advances, and current theoretical approaches for interpreting M-edge spectra. We further discuss a range of applications in catalysis, materials science, and coordination chemistry, highlighting the technique’s growing impact and potential for future studies.

M-edge XANES↗
DOE OSTI2022

In vitro investigation of protein assembly by combined microscopy and infrared spectroscopy at the nanometer scale

The nanoscale structure and dynamics of proteins on surfaces has been extensively studied using various imaging techniques, such as transmission electron microscopy and atomic force microscopy (AFM) in liquid environments. These powerful imaging techniques, however, can potentially damage or perturb delicate biological material and do not provide chemical information, which prevents a fundamental understanding of the dynamic processes underlying their evolution under physiological conditions. Here, we use a platform developed in our laboratory that enables acquisition of infrared (IR) spectroscopy and AFM images of biological material in physiological liquids with nanometer resolution in a cell closed by atomically thin graphene membranes transparent to IR photons. In this work, we studied the self-assembly process of S-layer proteins at the graphene-aqueous solution interface. The graphene acts also as the membrane separating the solution containing the proteins and Ca 2+ ions from the AFM tip, thus eliminating sample damage and contamination effects. The formation of S-layer protein lattices and their structural evolution was monitored by AFM and by recording the amide I and II IR absorption bands, which reveal the noncovalent interaction between proteins and their response to the environment, including ionic strength and solvation. Our measurement platform opens unique opportunities to study biological material and soft materials in general.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Temperature-dependent dielectric function of tantalum nitride formed by atomic layer deposition for tunnel barriers in Josephson junctions

Here, we report the dielectric functions of insulating tantalum nitride (TaN) films deposited by atomic layer deposition (ALD) on 300 mm Si/SiO 2 substrates to evaluate their suitability as tunnel barriers in tantalum-based Josephson junctions (JJs) for superconducting quantum circuits. Temperature-dependent ellipsometric angles were measured for ALD TaN films with nominal thicknesses of 13 and 25 nm at an incidence angle of 70°, over photon energy ranges of 0.03–0.7 eV (80–300 K) and 0.5–6.5 eV (80–600 K). These data were used to develop a dispersion model for insulating ALD TaN that incorporates a Tauc–Lorentz oscillator with an optical bandgap of 1.5–1.8 eV to describe interband transitions. The extracted dielectric function shows insulating behavior (mid-infrared transparency) at all temperatures and for both film thicknesses tested. In particular, ALD TaN does not exhibit infrared absorption due to free carriers, even at elevated temperatures, consistent with the insulating behavior required for a JJ tunnel barrier. Results from transmission electron microscopy (including selected area electron diffraction) and x-ray diffraction are also discussed. Sputter depth-profile x-ray photoelectron spectroscopy shows an N/Ta ratio of ∼1.2 throughout the film. The lower bandgap, low roughness, and thermal stability of ALD TaN compared to AlO x suggest the possibility of fabricating JJs with thicker barriers while achieving critical current densities required for qubits, enabling improved thickness and composition control, reduced topography, and resistance to aging.

36 MATERIALS SCIENCE↗
DOE OSTI2022

GeoSoilEnviroCARS (Sector 13) at the Advanced Photon Source: a comprehensive synchrotron radiation facility for Earth science research at ambient and extreme conditions

GeoSoilEnviroCARS (GSECARS) is a comprehensive analytical laboratory for Earth and environmental science research using X-ray beams from the Advanced Photon Source, Argonne National Laboratory. State-of-the-art instruments are available for (1) high-pressure/high- or low-temperature diffraction, total scattering, and spectroscopy (Brillouin, Raman, and VIS-IR) using the laser heated diamond anvil cell (DAC); (2) high-pressure/high-temperature diffraction, scattering, and imaging as well as acoustic emission (AE) and ultrasonics using the large-volume press (LVP); (3) powder, single crystal, and surface/interface diffraction; (4) X-ray absorption fine structure spectroscopy; (5) X-ray fluorescence microprobe analysis; and (6) microtomography. As shown here, experiments are facilitated by senior level staff who collaborate on all aspects of the analytical work including experiment design, sample preparation, data collection, data interpretation, and publication preparation. Both technical and scientific synergies occur as a result of the intimate association of the various techniques and scientists experienced in the applications of synchrotron radiation to Earth, environmental, and planetary science problems. The facility includes state-of-the-art instrumentation designed and built in-house, including custom X-ray optics, online and offline laser-based systems, specialized sample environments and positioning systems, as well as pixel-array and multi-crystal energy dispersive X-ray detectors, which are available to be shared among the experimental stations.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Metasurfaces with Multipolar Resonances and Enhanced Light–Matter Interaction

Metasurfaces, composed of engineered nanoantennas, enable unprecedented control over electromagnetic waves by leveraging multipolar resonances to tailor light–matter interactions. This review explores key physical mechanisms that govern their optical properties, including the role of multipolar resonances in shaping metasurface responses, the emergence of bound states in the continuum (BICs) that support high-quality factor modes, and the Purcell effect, which enhances spontaneous emission rates at the nanoscale. These effects collectively underpin the design of advanced photonic devices with tailored spectral, angular, and polarization-dependent properties. This review discusses recent advances in metasurfaces and applications based on them, highlighting research that employs full-wave numerical simulations, analytical and semi-analytic techniques, multipolar decomposition, nanofabrication, and experimental characterization to explore the interplay of multipolar resonances, bound and quasi-bound states, and enhanced light–matter interactions. A particular focus is given to metasurface-enhanced photodetectors, where structured nanoantennas improve light absorption, spectral selectivity, and quantum efficiency. By integrating metasurfaces with conventional photodetector architectures, it is possible to enhance responsivity, engineer photocarrier generation rates, and even enable functionalities such as polarization-sensitive detection. The interplay between multipolar resonances, BICs, and emission control mechanisms provides a unified framework for designing next-generation optoelectronic devices. This review consolidates recent progress in these areas, emphasizing the potential of metasurface-based approaches for high-performance sensing, imaging, and energy-harvesting applications.

Kerker effect↗
DOE OSTI2023

Anisotropic Excitons Reveal Local Spin Chain Directions in a van der Waals Antiferromagnet

A long‐standing pursuit in materials science is to identify suitable magnetic semiconductors for integrated information storage, processing, and transfer. Van der Waals magnets have brought forth new material candidates for this purpose. Recently, sharp exciton resonances in antiferromagnet NiPS 3 have been reported to correlate with magnetic order, that is, the exciton photoluminescence intensity diminishes above the Néel temperature. Here, it is found that the polarization of maximal exciton emission rotates locally, revealing three possible spin chain directions. This discovery establishes a new understanding of the antiferromagnet order hidden in previous neutron scattering and optical experiments. Furthermore, defect‐bound states are suggested as an alternative exciton formation mechanism that has yet to be explored in NiPS 3 . The supporting evidence includes chemical analysis, excitation power, and thickness dependent photoluminescence and first‐principles calculations. This mechanism for exciton formation is also consistent with the presence of strong phonon side bands. This study shows that anisotropic exciton photoluminescence can be used to read out local spin chain directions in antiferromagnets and realize multi‐functional devices via spin‐photon transduction.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Structure of high-lying levels populated in the 96 Y → 96 Zr β decay

The nature of the high-lying final levels of the 96 Y gs β decay, one of the three most important contributors to the high-energy reactor antineutrino spectrum, has been investigated in high-resolution γ-ray spectroscopy following the β decay as well as in a campaign of inelastic photon scattering experiments. The comprehensive approach establishes 1 - levels associated with the Pygmy Dipole Resonance as high-lying final levels in the β decay. Branching ratios extracted from β decay complement photon scattering and allow the absolute E1 excitation strength to be determined for levels populated in both reactions. The combined data represents a comprehensive approach to the wavefunction of the 1 - levels below the Qβ value, which are investigated in the Quasiparticle Phonon Model. The calculations reveal that the components populated in β decay contribute only with small amplitudes to the complex wavefunction of these 1 - levels. A comparison of the β decay results to data from total absorption γ -ray spectroscopy demonstrates a good agreement between both measurements.

Pygmy dipole resonance↗