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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

J -Resolved Molecular Fingerprinting by Parahydrogen Hyperpolarized Low-Field NMR

A J-resolved spectroscopy that depends on homonuclear scalar coupling in the strong-coupling regime and heteronuclear coupling in the weak regime expands complex peak patterns to a second axis. Hyperpolarization by Signal Amplification by Reversible Exchange (SABRE) enables the spectroscopy at a low magnetic field of 0.82 mT. Overlapping peaks of molecules such as 3-fluoropyridine and 3,5-difluoropyridine are resolved. Density matrix simulations of the 1 H and 19 F spins indicate a strong dependence on the signs and values of the J-coupling constants, including the homonuclear couplings that are not directly observable. The best matching peak positions and intensities predict coupling constants, including couplings between chemically equivalent nuclear spins, ranging in magnitude from 0.4 to 9.0 Hz for the two molecules. Simulations of other spin systems show unique patterns for molecules containing 1 H and 19 F or 13 C. The dependence of the J-resolved peak patterns on all coupling constants in a spin system presents a new modality for portable and inexpensive identification of molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

What dictates soft clay-like lithium superionic conductor formation from rigid salts mixture

Abstract Soft clay-like Li-superionic conductors, integral to realizing all-solid-state batteries, have been recently synthesized by mixing rigid-salts. Here, through computational and experimental analysis, we clarify how a soft clay-like material can be created from a mixture of rigid-salts. Using molecular dynamics simulations with a deep learning-based interatomic potential energy model, we uncover the microscopic features responsible for soft clay-formation from ionic solid mixtures. We find that salt mixtures capable of forming molecular solid units on anion exchange, along with the slow kinetics of such reactions, are key to soft-clay formation. Molecular solid units serve as sites for shear transformation zones, and their inherent softness enables plasticity at low stress. Extended X-ray absorption fine structure spectroscopy confirms the formation of molecular solid units. A general strategy for creating soft clay-like materials from ionic solid mixtures is formulated.

25 ENERGY STORAGE↗
NASA NTRS1973

A comment on the measurement of atmospheric density by absorption of Lyman-alpha.

It is shown that the absorption cross section for molecular oxygen at Lyman alpha is about 0.8 times 10 to the minus twentieth power sq cm. It is pointed out that, for application of absorption spectroscopy to the measurement of molecular oxygen density in the atmosphere, no correction for the variation of cross section with wavelength is necessary.

Smith, L. G.↗
NASA NTRS1988

Coherent light scattering spectroscopy for supersonic flow measurements

A unified discussion on coherent light scattering spectroscopy and its spectral dependence on molecular gas velocity, temperature and density is presented. The feasibility of using coherent Raman spectroscopy techniques for nonintrusive measurements of supersonic flow parameters is demonstrated and recent laboratory as well as wind tunnel experiments are reviewed. In addition, the advantages of using coherent Rayleigh-Brillouin spectroscopy for measuring high pressure flows are discussed.

She, C. Y.↗
DOE OSTI2021

Anomalous fast atomic dynamics in bulk metallic glasses

It is believed that the strong glass formers tend to be dense packing and have rather slow atomic dynamics. Here, we report that the anomalous fast atomic dynamics exist in an Au 55 Cu 20 Ag 5 Si 20 metallic glass (MG) with good glass forming ability (GFA) by combining X-ray photon correlation spectroscopy measurements with ab initio molecular dynamics simulations. The fast dynamics are mainly originated from the increased mobility of Cu atoms by Ag addition. Ag atoms are inclined to locate at Cu-centered <0, 2, 8, 1> motifs, which slow or accelerate the dynamics of shell Cu atoms, depending on whether Ag atoms appear at the first shells or not, leading to the formation of structural heterogeneity at the atomic level. The results enrich the understanding of atomic dynamics in Cue-Ag-containing MGs and will trigger more studies on the dynamics-GFA relationship in MGs.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Kβ X-ray Emission Spectroscopy of Cu(I)-Lytic Polysaccharide Monooxygenase: Direct Observation of the Frontier Molecular Orbital for H 2 O 2 Activation

Lytic polysaccharide monooxygenases (LPMOs) catalyze the degradation of recalcitrant carbohydrate polysaccharide substrates. These enzymes are characterized by a mononuclear Cu(I) active site with a three-coordinate T-shaped “His-brace” configuration including the N-terminal histidine and its amine group as ligands. Here, this study explicitly investigates the electronic structure of the d 10 Cu(I) active site in a LPMO using Kβ X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the 3d/p mixing required for intensity in the Kβ valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kβ XES data are correlated to density functional theory (DFT) calculations to define the bonding, and in particular, the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H 2 O 2 O–O bond and understand the contribution of this FMO to the low barrier of this reaction and how the geometric and electronic structure of the Cu(I)-LPMO site is activated for rapid reactivity with H 2 O 2 .

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

Thickness-dependent spin bistable transitions in single-crystalline molecular 2D material

Abstract The advent of two-dimensional (2D) crystals has led to numerous scientific breakthroughs. Conventional 2D systems have in-plane covalent bonds and a weak out-of-plane van-der-Waals bond. Here we report a new type of 2D material composed of discrete magnetic molecules, where anisotropic van-der-Waals interactions bond the molecules into a 2D packing. Through mechanical exfoliation, we can obtain single-crystalline molecular monolayers, which can be readily integrated into other 2D systems. Optical spectroscopy suggests the few-layered molecules preserve the temperature-induced spin-crossover switching observed in the bulk form but show a drastic increase in thermal hysteresis unique to these thin 2D molecule assemblies. The trapping of spin bistability with decreasing layer number can arise from domain wall dynamics in reduced dimensions. Our results establish molecular solids with strong anisotropy of intermolecular interactions as precursors to a new class of 2D materials, affording possibilities to control molecular functionalities through substrate and interlayer interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nitrogen in black phosphorus structure

Group V elements in crystal structure isostructural to black phosphorus with unique puckered two-dimensional layers exhibit exciting physical and chemical phenomena. However, as the first element of group V, nitrogen has never been found in the black phosphorus structure. Here, we report the synthesis of the black phosphorus–structured nitrogen at 146 GPa and 2200 K. Metastable black phosphorus–structured nitrogen was retained after quenching it to room temperature under compression and characterized in situ during decompression to 48 GPa, using synchrotron x-ray diffraction and Raman spectroscopy. We show that the original molecular nitrogen is transformed into extended single-bonded structure through gauche and trans conformations. Raman spectroscopy shows that black phosphorus–structured nitrogen is strongly anisotropic and exhibits high Raman intensities in two A g normal modes. Synthesis of black phosphorus–structured nitrogen provides a firm base for exploring new type of high-energy-density nitrogen and a new direction of two-dimensional nitrogen.

58 GEOSCIENCES↗
DOE OSTI2020

Identifying the Molecular Edge Termination of Exfoliated Hexagonal Boron Nitride Nanosheets with Solid-State NMR Spectroscopy and Plane-Wave DFT Calculations

Hexagonal boron nitride nanosheets (h-BNNS), the isoelectronic analog to graphene, have received interest over the past decade due to their high thermal oxidative resistance, high bandgap, catalytic activity, and low cost. The functional groups that terminate boron and nitrogen zigzag and/or armchair edges directly affect their chemical, physical, and electronic properties. However, an understanding of the molecular edge termination present in h-BNNS is lacking. Here, high-resolution magic-angle spinning (MAS) solid-state NMR (SSNMR) spectroscopy, and plane-wave density-functional theory (DFT) calculations are used to determine the molecular edge termination in exfoliated h-BNNS. 1 H → 11 B cross-polarization MAS (CPMAS) SSNMR spectra of h-BNNS revealed multiple hydroxyl/oxygen coordinated boron edge sites that were not detectable in direct excitation experiments. A dynamic nuclear polarization (DNP)-enhanced 1 H → 15 N CPMAS spectrum of h-BNNS displayed four distinct 15 N resonances while a 2D 1 H{ 14 N} dipolar-HMQC spectrum acquired with fast MAS revealed three distinct 14 N environments. Plane-wave DFT calculations were used to construct model edge structures and predict the corresponding 11 B, 14 N and 15 N SSNMR spectra. Comparison of the experimental and predicted SSNMR spectra confirms that zigzag and armchair edges with both amine and boron hydroxide/oxide termination are present. The detailed characterization of h-BNNS molecular edge termination will prove useful for many material science applications. The techniques outlined here should also be applicable to understand the molecular edge terminations in other 2D materials

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electronic spectroscopy and ionization potentials for YbOH and YbOCH 3

The polyatomic molecules YbOH and YbOCH 3 have been recognized as being of potential value for spectroscopic experiments that explore charge-parity and time reversal symmetry violation effects. These measurements require very high precision, which, in turn, will necessitate that the molecules be manipulated at ultra-cold temperatures. Both YbOH and YbOCH 3 have electronic transitions that appear suitable for laser cooling ($\tilde{A}$ 2 Π 1/2 -$\tilde{X}$ 2 Σ + and $\tilde{A}$2E 1/2 -$\tilde{X}$ 2 A 1 , respectively) but the currently available spectroscopic data is not sufficient to determine the extent to which population leaks may compromise the optical cooling processes. A further complication is that the quantum states of interest for these measurements will need to be selectively populated. The $\tilde{A}$-$\tilde{X}$ band systems of both YbOH and YbOCH 3 show evidence of vibronic perturbations, such that there are unassigned vibronic features at energies that are just above the origin bands. Here, in the present study we have recorded spectra for the $\tilde{A}$ 2 Π 1/2 -$\tilde{X}$ 2 Σ + transition of jet-cooled YbOD to facilitate the vibronic assignments. In addition, spectra for the $\tilde{B}$ 2 Σ + - $\tilde{X}$ 2 Σ + transition of YbOH were recorded, establishing the origin band at 20473.8 cm -1 . Previously, the reaction of Yb with CH 3 OH has been used to generate gas-phase YbOCH 3 . As this reaction also yields YbOH, there have been complications in spectroscopic studies of YbOCH 3 due to overlap of the $\tilde{A} -\tilde{X}$ band systems. To identify specific regions of overlap, resonantly enhanced two-photon ionization spectra were recorded using mass-resolved detection of the YbOH + and YbOCH 3 + ions. These data confirmed the overlap of vibronic bands near 17640 and 17680 cm -1 . Two-photon ionization spectroscopy also provided accurate ionization energies of IE(YbOH)=45788(10) and IE(YbOCH 3 )=45283(10) cm -1 . The IE for YbOH is relevant to problems encountered in previous attempts to determine the bond dissociation energy of YbOH + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Transmission Spectroscopy for the Warm Sub-Neptune HD 3167c: Evidence for Molecular Absorption and a Possible High-metallicity Atmosphere

We present a transmission spectrum for the warm (500−600 K) sub-Neptune HD 3167c obtained using the Hubble Space Telescope Wide Field Camera 3 infrared spectrograph. We combine these data, which span the 1.125–1.643 μm wavelength range, with broadband transit measurements made using Kepler/K2 (0.6–0.9 μm) and Spitzer/IRAC (4–5 μm). We find evidence for absorption by at least one of H{sub 2}O, HCN, CO{sub 2}, and CH{sub 4} (Bayes factor 7.4; 2.5σ significance), although the data precision does not allow us to unambiguously discriminate between these molecules. The transmission spectrum rules out cloud-free hydrogen-dominated atmospheres with metallicities ≤100× solar at >5.8σ confidence. In contrast, good agreement with the data is obtained for cloud-free models assuming metallicities >700× solar. However, for retrieval analyses that include the effect of clouds, a much broader range of metallicities (including subsolar) is consistent with the data, due to the degeneracy with cloud-top pressure. Self-consistent chemistry models that account for photochemistry and vertical mixing are presented for the atmosphere of HD 3167c. The predictions of these models are broadly consistent with our abundance constraints, although this is primarily due to the large uncertainties on the latter. Interior structure models suggest that the core mass fraction is >40%, independent of a rock or water core composition, and independent of atmospheric envelope metallicity up to 1000× solar. We also report abundance measurements for 15 elements in the host star, showing that it has a very nearly solar composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

From inert gas to fertilizer, fuel and fine chemicals: N 2 reduction and fixation

The 100th anniversary of a leading nitrogen fixation technology developer like CASALE SA is a reason to reflect over the 20th century successful solution of the problem of world food supply, and to look out for solutions for sustainable developments with respect to ammonia production. Here, we review the role of nitrogen as essential chemical constituent in photosynthesis and biology, and component of ammonia as it is used as fertilizer for primary production by photosynthesis for farming and food supply and its future role as energy carrier. While novel synthesis methods and very advanced synchrotron based x-ray analytical techniques are being developed, we feel it is important to refer to the historical and economical context of nitrogen. The breaking of the N≡N triple bond remains a fundamental chemical and energetic problem in this context. We review the electrochemical ammonia synthesis as an energetically and environmentally benign method. Two relatively novel X-ray spectroscopy methods, which are relevant for the molecular understanding of the catalysts and biocatalysts, i.e. soft X-ray absorption spectroscopy and nuclear resonant vibration spectroscopy are presented. We illustrate the perceived reality in fertilizer usage on the field, and fertilizer production in the factory complex with photos and thus provide a contrast to the academic view of the molecular process of ammonia function and production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Spectroscopy and multivariate analyses applications related to solid rocket nozzle bondline

Chemical composition and molecular orientation define the properties of materials. Information related to chemical composition and molecular configuration is obtained by various forms of spectroscopy. Software algorithms developed for multivariate analyses, expert systems, and Artificial Intelligence (AI) are used to conduct repetitive operations. The techniques are believed to be of particular significance toward achieving TQM objectives. The objective was to obtain information related to the quality of the bondline in the solid rocket motor, SRM, nozzle. Hysol 934 NA, a room temperature curing epoxide resin, is used as the bonding agent. A good bond requires that the adhesive be placed on a properly prepared metal surface, the adhesives Part A and B be mixed in appropriate ratio from material within shelf life specifications. Spectroscopic data was obtained for surfaces prepared according to specifications, contaminated metal surfaces, samples of the epoxide adhesive at times that represent shelf aging from 3 months to 2 years, several mix ratio of A to B, and curing material. Temperature was found to be a significant factor. The study concentrated on pot life and mix ratio.

Arendale, W. F.↗
DOE OSTI2020

Evidence for trap-assisted Auger recombination in MBE grown InGaN quantum wells by electron emission spectroscopy

We report on the direct measurement of hot electrons generated in the active region of blue light-emitting diodes grown by ammonia molecular beam epitaxy by electron emission spectroscopy. The external quantum efficiency of these devices is <1% and does not droop; thus, the efficiency losses from the intrinsic, interband, electron-electron-hole, or electron-hole-hole Auger should not be a significant source of hot carriers. Here, the detection of hot electrons in this case suggests that an alternate hot electron generating process is occurring within these devices, likely a trap-assisted Auger recombination process.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Tantalum oxide and nitride spectral features from a laser-produced plasma

Here, we report measurements of time-resolved Ta, TaO and TaN emission spectroscopic signatures from a laser-produced plasma. Plasmas were generated using 1064 nm, 6 ns pulses from an Nd:YAG laser focused onto a pure Ta metal target in a gaseous environment with varying percentages of O 2 /N 2 for controlling gas-phase oxidation/plasma chemistry. Time-resolved analysis showed that Ta oxide emission is prominent at later times in plasma evolution, whereas strong atomic emission is present at early times in air. Emission spectral features as a function of O 2 partial pressure showed that TaO emission intensity increases, while the peak intensity of TaO appears earlier with increasing O 2 availability. We also report emission spectra of TaN, and show that plasma chemistry favors TaO formation instead of TaN when O 2 is present in the environment.

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

Mechanistic studies of small molecule ligands selective to RNA single G bulges

Abstract Small-molecule RNA binders have emerged as an important pharmacological modality. A profound understanding of the ligand selectivity, binding mode, and influential factors governing ligand engagement with RNA targets is the foundation for rational ligand design. Here, we report a novel class of coumarin derivatives exhibiting selective binding affinity towards single G RNA bulges. Harnessing the computational power of all-atom Gaussian accelerated molecular dynamics simulations, we unveiled a rare minor groove binding mode of the ligand with a key interaction between the coumarin moiety and the G bulge. This predicted binding mode is consistent with results obtained from structure-activity relationship studies and transverse relaxation measurements by nuclear magnetic resonance spectroscopy. We further generated 444 molecular descriptors from 69 coumarin derivatives and identified key contributors to the binding events, such as charge state and planarity, by lasso (least absolute shrinkage and selection operator) regression. Our work deepened the understanding of RNA-small molecule interactions and integrated a new framework for the rational design of selective small-molecule RNA binders.

Biochemistry & Molecular Biology↗
NASA NTRS2014

X-Ray Absorption near Edge Structure Spectroscopic Study of Hayabusa Category 3 Carbonaceous Particles

Analyses with a scanning transmission x-ray microscope (STXM) using x-ray absorption near edge structure (XANES) spectroscopy were applied for the molecular characterization of two kinds of carbonaceous particles of unknown origin, termed category 3, which were collected from the Hayabusa spacecraft sample catcher. Carbon-XANES spectra of the category 3 particles displayed typical spectral patterns of heterogeneous organic macromolecules; peaks corresponding to aromatic/olefinic carbon, heterocyclic nitrogen and/or nitrile, and carboxyl carbon were all detected. Nitrogen-XANES spectra of the particles showed the presence of N-functional groups such as imine, nitrile, aromatic nitrogen, amide, pyrrole, and amine. An oxygen-XANES spectrum of one of the particles showed a ketone group. Differences in carbon- and nitrogen-XANES spectra of the category 3 particles before and after transmission electron microscopic (TEM) observations were observed, which demonstrates that the carbonaceous materials are electron beam sensitive. Calcium-XANES spectroscopy and elemental contrast mapping identified a calcium carbonate grain from one of the category 3 particles. No fluorine-containing molecular species were detected in fluorine-XANES spectra of the particles. The organic macromolecular features of the category 3 particles were distinct from commercial and/or biological ‘fresh (non-degraded)’ polymers, but the category 3 molecular features could possibly reflect degradation of contaminant polymer materials or polymer materials used on the Hayabusa spacecraft. However, an extraterrestrial origin for these materials cannot currently be ruled out.

Asteroides↗