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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 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Equation of state and hyperfine parameters of high-spin bridgmanite in the Earth’s lower mantle by synchrotron X-ray diffraction and Mössbauer spectroscopy

In this study, we performed synchrotron X-ray diffraction (XRD) and Mössbauer spectroscopy (SMS) measurements on two single-crystal bridgmanite samples [ Embedded Image and Embedded Image ] to investigate the combined effect of Fe and Al on the hyperfine parameters, lattice parameters, and equation of state (EoS) of bridgmanite up to 130 GPa. Our SMS results show that Fe2+ and Fe3+ in Bm6 and Al-Bm11 are predominantly located in the large pseudo-dodecahedral sites (A-site) at lower-mantle pressures. The observed drastic increase in the hyperfine quadrupole splitting (QS) between 13 and 32 GPa can be associated with an enhanced local distortion of the A-site Fe2+ in Bm6. In contrast to Bm6, the enhanced lattice distortion and the presence of extremely high QS values of Fe2+ are not observed in Al-Bm11 at high pressures. Our results here support the notion that the occurrence of the extremely high QS component of approximately 4 mm/s in bridgmanite is due to the lattice distortion in the high-spin (HS) A-site Fe2+, instead of the occurrence of the intermediate-spin state. Both A-site Fe2+ and Fe3+ in Bm6 and Al-Bm11 remain in the HS state at lower-mantle pressures. Together with XRD results, we present the first experimental evidence that the enhanced lattice distortion of A-site Fe2+ does not cause any detectable variation in the EoS parameters, but is associated with anomalous variations in the bond length, tilting angle, and shear strain in the octahedra of Bm6. Analysis of the obtained EoS parameters of bridgmanite at lower-mantle pressures indicates that the substitution of Fe in bridgmanite will cause an enhanced density and a reduced bulk sound velocity (VΦ), whereas the Al and Fe substitution has a reduced effect on density and a negligible effect on VΦ. These experimental results provide new insight into the correlation between lattice, hyperfine, and EoS parameters of bridgmanite in the Earth’s lower mantle.

58 GEOSCIENCES↗
DOE OSTI2025

Combining Theory and Experiment to Map the Atomic-Level Structure–Energy Pathways of Adsorbate-Mediated Phase Changes in a Cooperatively Flexible Metal–Organic Framework

An important subclass of metal–organic frameworks (MOFs) exhibits cooperative flexibility, wherein individual crystallites undergo global structural phase changes in response to external stimuli. Where cooperative flexibility results in reversible changes between crystalline states of distinct accessible porosity, these frameworks can exhibit rare yet desirable behaviors that cannot be explained by local dynamics alone. Yet, the chemical and structural origins of cooperative flexibility and how frameworks undergo these reversible phase changes at the atomic level remain poorly understood. Deliberate design for specific applications is therefore exceedingly difficult, and there is great impetus to develop a fundamental understanding of this phenomenon. Here, an effective and widely accessible computational approach is developed, which is designed to provide microscopic resolution via direct comparison to experimental data along the desorption-guided pathway. The strategy is applied to explain the desorption-induced phase change in an experimentally well-characterized framework, CdIF-13 (sod-Cd(benzimidazolate)2), where experiment alone was unable to resolve the atomistically detailed phase change landscape. Our findings reveal that the cooperative phase change pathways are adsorbate dependent with thermodynamics of intermediate structural states dictated by a nuanced interplay of ligand orientation, skeletal symmetry, and modes of surface adsorption. The results reveal that this isotropically flexible framework is “chaperoned” through a complex energy landscape by specific adsorbates, revealed by the reported computational approach with atomic-level insight and validated by experimentally determined structures. Thus, this work facilitates both understanding and future design of flexible materials for applications in gas storage, transport, delivery, and separation technologies.

03 NATURAL GAS↗
DOE OSTI2010

2s photoionization and subsequent Auger cascade in atomic Si

The 2s photoionization and subsequent Auger transition cascade in atomic Si were studied by means of synchrotron-radiation-induced electron spectroscopy. After the 2s photoionization, the core hole states decay predominantly by a two-step Auger transition cascade into the triply ionized [Ne]nl states. The ionization channels of the 2s core-ionized Si{sup +} atoms to Si{sup 3+} ions were observed by measuring the conventional Auger electron spectra of the L{sub 1}-L{sub 2,3}M Coster-Kronig transitions and the L{sub 2,3}M-MMM Auger transitions. The observed L{sub 1}-L{sub 2,3}M and L{sub 2,3}M-MMM Auger spectra were analyzed by means of extensive multiconfiguration Dirac-Fock computations. We found that the electron correlation plays a prominent role in the Auger cascade, especially for the final-step Auger L{sub 2,3}M-MMM spectrum. Additionally, it was seen that the L{sub 2,3}M-MMM Auger spectrum of Si includes more Auger groups than the isoelectronic L{sub 2,3}-MM Auger spectrum of Al. Thus, more information on the intermediate ionic states is obtained if they are produced by Auger cascade rather than by direct photoionization.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2013

Spectroscopy of the three-photon laser excitation of cold Rubidium Rydberg atoms in a magneto-optical trap

The spectra of the three-photon laser excitation 5S{sub 1/2} {yields} 5P{sub 3/2} {yields} 6S{sub 1/2}nP of cold Rb Rydberg atoms in an operating magneto-optical trap based on continuous single-frequency lasers at each stage are studied. These spectra contain two partly overlapping peaks of different amplitudes, which correspond to coherent three-photon excitation and incoherent three-step excitation due to the presence of two different ways of excitation through the dressed states of intermediate levels. A four-level theoretical model based on optical Bloch equations is developed to analyze these spectra. Good agreement between the experimental and calculated data is achieved by introducing additional decay of optical coherence induced by a finite laser line width and other broadening sources (stray electromagnetic fields, residual Doppler broadening, interatomic interactions) into the model.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Mechanistic Insights into the Demethylation of Lignin‐Derived Structures Using Protic Ionic Liquids: A Density Functional Theory Study

Lignin valorization is restricted by the stability of its methoxy groups, creating a critical need for efficient demethylation strategies. Here, in this study, density functional theory (DFT) is employed to dissect the mechanistic pathways of demethylation in lignin model compounds, guaiacol and syringol, using protic ionic liquids (PILs) that act as both solvent and catalyst. Conductor‐like Screening Model for Real Solvents (COSMO‐RS) analysis identifies monoethanolammonium acetate ([MEOA][Ace]) as the most promising medium, attributed to its strong hydrogen bonding network and solvation ability. By integrating implicit and explicit solvation models, it is revealed that an acid‐catalyzed hydrolytic mechanism governs demethylation, with PILs stabilizing crucial transition states and intermediates. Complementary electronic structure evaluations, including highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO‐LUMO) gap analysis, charge distribution, and electrostatic potential mapping, demonstrate how PILs lower energetic barriers and enhance reactivity. To simulate realistic environments, this study is extended to lignin dimer complexes with varying water content, uncovering how water‐bridged solvation reverses demethylation preference from guaiacyl to syringyl units. This mechanistic shift aligns with experimental observations showing faster S‐unit reactivity in hydrated systems. Together, these findings provide atomic‐level insight into lignin demethylation dynamics and highlight how tuning acid concentration in PILs can accelerate kinetics, enabling a rational pathway toward next‐generation biomass conversion technologies.

COSMO-RS↗
DOE OSTI2025

Plasma Assisted Combustion and Chemical Processing: Chapter 9 - Plasma Diagnostics

Plasma dynamics and chemistry have a broad range of timescales from picoseconds to milliseconds. In addition, it involves nonequilibrium energy transfer between electrons, ions, electronically and vibrationally excited states, radicals, intermediate species, and reactants and products as well as surface charges and chemistry. To understand plasma physics and chemistry, it is essential to conduct time and space resolved, quantitative detection of nonequilibrium temperature distributions, electron energy and number density, electric field, and species concentrations. There are enormous publications and review articles on this subject. The focus of this chapter is to be placed on the most recent progress in gas phase plasma properties and chemistry, especially on optical emission spectroscopy, laser absorption spectroscopy, Faraday rotational spectroscopy, Raman and Thompson scattering, femtosecond and picosecond (fs/ps) coherent anti-Stokes Raman scattering (CARS) spectroscopy, and electric field-induced second harmonic generation methods.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Mini volume collapse as evidence for a three-body magnetic polaron in S m 1 - x E u x S

Samarium sulfide (SmS) is a nonmagnetic narrow-gap (0.06 eV) semiconductor that undergoes a transition to a metallic intermediate valence state at 6.5 kbar. Europium sulfide (EuS) is a ferromagnetic semiconductor with a Curie temperature of 16 K and a gap of 1.6 eV. Here we present a study of the lattice constant, magnetic susceptibility, and resistivity of the substitution series Sm 1-x Eu x S for 0 < x < 1. We observe a smooth interpolation of magnetic and transport behavior across the series, consistent with a virtual crystal scenario and Vegard’s law. Surprisingly, however, the lattice constant deviates below Vegard’s law in a manner that suggests parametric control of the Sm-Sm distance by the Eu moment in the manner of a magnetic polaron.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Phase Synergy Enables Low‐Power Ferroelectric Switching in HfO 2 Epitaxial Films

HfO 2 -based ferroelectric materials have emerged as leading candidates for next-generation non-volatile memory technologies, owing to their nanoscale robust ferroelectricity and complementary metal–oxide–semiconductor (CMOS) compatibility. However, challenges and debates persist in advancing and comprehensively understanding their ferroelectric behavior. In particular, conventional approaches typically regard non-ferroelectric phases as detrimental and primarily focus on suppressing their formation, yet overlooking their potentially synergistic contributions—particularly those of the tetragonal (T) phase. Here, we unambiguously clarify the beneficial role of the T-phase and introduce a phase-boundary engineering strategy that deliberately harnesses it to enhance ferroelectricity in HfO 2 films. By stabilizing optimal coherent boundaries between ferroelectric orthorhombic (O) and T phases in epitaxial La-doped HfO 2 films, we achieve significant improvements in ferroelectric properties—doubling the remanent polarization (P r ∼ 30 µC/cm 2 ) and substantially reducing the coercive field (E c ∼ 3 MV/cm) by 30% compared to low-La doped samples without such boundaries. Atomic-scale electron microscopy reveals the structural nature of the atomically sharp, coherent O–T boundaries. Combined with deep-learning enhanced molecular dynamics simulations, our results unravel that these boundaries facilitate intermediate polarization states that lower the switching energy barrier. Consequently, phase coexistence shifts from an inherent drawback to a tunable design element, offering a broadly applicable route to ultra-low-power HfO 2 -based nanoelectronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Study of the e + e - → π + π - ω process at center-of-mass energies between 4.0 and 4.6 GeV

Using 15.6 fb -1 of e + e - collision data collected at twenty-four center-of-mass energies from 4.0 to 4.6 GeV with the BESIII detector, the helicity amplitudes of the process e+e- → π+π-ω are analyzed for the first time. Born cross section measurements of two-body intermediate resonance states with statistical significance greater than 5σ are presented, such as f 0 (500), f 0 (980), f 2 (1270), f 0 (1370), b 1 (1235) ± , and ρ(1450) ± . In addition, evidence of a resonance state in e + e - → π + π - ω production is found. The mass of this state obtained by line shape fitting is about 4.2 GeV/c 2 , which is consistent with the production of ψ(4160) or Y(4220).

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2017

Transition-metal redox evolution in LiNi 0.5 Mn 0.3 Co 0.2 O 2 electrodes at high potentials

The mixed transition-metal layered compound, LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532), is a promising high-energy cathode material. However, the required high-voltage (>4.3 V) cycling is accompanied by a rapid capacity fade associated with a complex redox mechanism that has not been clarified. Here in this paper, we report soft x-ray absorption spectroscopy of NMC532 electrodes, both pristine and those charged to 4.2, 4.35, or 4.5 V in graphite/NMC532 cells. A quantitative sXAS analysis shows that about 20% of the nickel exists as Ni 4+ in the as-synthesized NMC532. The Ni redox reaction contributes only to the experimental capacity obtained below 4.2 V, while Co redox reactions take place throughout the entire electrochemical cycling up to 4.5 V. In contrast to the changing ratio of the well-defined Ni 2+ , Ni 3+ and Ni 4+ ions, Co always displays ill-defined intermediate valence states in the charged NMC532 electrodes. This indicates an itinerant electron system in NMC electrodes related to the improved rate performance through Co doping. Furthermore, about 20% of Ni 2+ is found on the electrode surface at the high potential, which suggests that the electrode surface has either gone through surface reconstruction or reacted with the electrolyte at high voltage.

25 ENERGY STORAGE↗
DOE OSTI2012

High thermoelectric performance of In, Yb, Ce multiple filled CoSb{sub 3} based skutterudite compounds

Filling voids with rare earth atoms is an effective way to lowering thermal conductivity which necessarily enhances thermoelectric properties of skutterudite compounds. Yb atom is one of the most effective species among the rare earth atoms for filling the voids in the skutterudite structure due to a large atomic mass, radius and it is intermediate valence state. In this work, we aim to find the best filling partners for Yb using different combinations of Ce and In as well as to optimize actual filling fraction in order to achieve high values of ZT. The traditional method of synthesis relying on melting-annealing and followed by spark plasma sintering was used to prepare all samples. The thermoelectric properties of four samples of Yb{sub 0.2}In{sub 0.2}Co{sub 4}Sb{sub 12}, Yb{sub 0.2}Ce{sub 0.15}Co{sub 4}Sb{sub 12}, Yb{sub 0.2}Ce{sub 0.15}In{sub 0.2}Co{sub 4}Sb{sub 12}, and Yb{sub 0.3}Ce{sub 0.15}In{sub 0.2}Co{sub 4}Sb{sub 12} (nominal) were examined based on the Seebeck coefficient, electrical conductivity, thermal conductivity, and Hall coefficient. Hall coefficient and Seebeck coefficient signs confirm that all samples are n-type skutterudite compounds. Carrier density increases with the increasing Yb+Ce content. A high power factor value of 57.7 {mu}W/K{sup 2}/cm for Yb{sub 0.2}Ce{sub 0.15}Co{sub 4}Sb{sub 12} and a lower thermal conductivity value of 2.82 W/m/K for Yb{sub 0.2}Ce{sub 0.15}In{sub 0.2}Co{sub 4}Sb{sub 12} indicate that small quantities of Ce with In may be a good partner to Yb to reduce the thermal conductivity further and thus enhance the thermoelectric performance of skutterudites. The highest ZT value of 1.43 was achieved for Yb{sub 0.2}Ce{sub 0.15}In{sub 0.2}Co{sub 4}Sb{sub 12} triple-filled skutterudite at 800 K. - Graphical abstract: Thermoelectric figure of merit of Yb{sub x}In{sub y}Ce{sub z}Co{sub 4}Sb{sub 12} (0{<=}x,y,z{<=}0.18 actual) compounds versus temperature. Highlights: Black-Right-Pointing-Pointer TE properties of Yb,In,Ce multiple-filled Yb{sub x}In{sub y}Ce{sub z}Co{sub 4}Sb{sub 12} skutterudites were investigated. Black-Right-Pointing-Pointer Thermal conductivity is strongly suppressed by multiple filling of Yb, Ce and In. Black-Right-Pointing-Pointer Small amounts of Ce and In with Yb are beneficial for the enhancement of TE performance. Black-Right-Pointing-Pointer The highest ZT=1.43 was achieved with Yb{sub 0.07}In{sub 0.094}Ce{sub 0.065}Co{sub 4}Sb{sub 11.92} at 800 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Evaluation of solid solution formation between ThO2 and δ-Bi2O3 by molecular precursor route

Highlights: • Molecular precursor route for the solid solution evaluation of ThO{sub 2}-BiO{sub 1.5}. • Up to 60 mol % of Bi{sup 3+} could be dissolved in fluorite structured ThO{sub 2}. • Oxygen vacancies manifested as defect bands after Bi{sup 3+} incorporation. • Narrowing of direct band gap with increasing Bi{sup 3+} concentration. - Abstract: The high chelating ability of nitrilotriacetic acid has been advantageously utilized to prepare molecular precursors containing thorium and bismuth. This aided to determine the extent of solid solution formation between thoria and δ-Bi{sub 2}O{sub 3} in fluorite structure by calcining the precursors in air. Up to 60 atomic % of Bi{sup 3+} could be substituted for Th{sup 4+} in fluorite structure beyond which phase separation occurred. Slight increase in cubic lattice constant was observed with increasing bismuth content along with indication of increased tensile strain of lattice. Porous morphology and presence of bismuth in calcined samples were confirmed from SEM and EDX measurements. Defect bands emerged in the Raman spectra near 590 cm{sup −1} in addition to a fluorite band near 460 cm{sup −1} for the bismuth substituted samples. Intermediate energy states were formed by the substitution of Bi{sup 3+} for Th{sup 4+} arising possibly from oxygen vacancies and it resulted in narrowing of direct band gap.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Interplay of Crystal Structure and Magnetic Properties of the Eu 5.08-x Sr x Al 3 Sb 6 Solid Solution

Zintl phases containing rare-earth metals have gained attention due to their magnetic, electronic, and thermoelectric properties. Eu 5.08 Al 3 Sb 6 is a new structure type (monoclinic space group C2/m) that can be described as a pseudorock-salt EuSb motif with the Eu-centered Sb octahedra at the origin of the unit cell, and on the C-face center, containing either Eu (8%) or an Al 4 tetrahedron modeled as a dual tetrahedron (37.5%). The complete solid solution of Eu 5.08–x Sr x Al 3 Sb 6 can be prepared; however, the cation totals vacillate from 5 to 5.24 depending on the Al content. Al K-edge XANES shows a shift to higher energy relative to the Al metal but at slightly lower energy relative to AlSb, indicating an intermediate oxidation state closer to +3 than 0. The lack of an Al K-edge shift with the incorporation of Sr suggests that changes in Sr content do not have a meaningful impact on the electronics of the Al tetrahedra. Investigation of the solid solution structures provides evidence for classifying this structure type as a polar intermetallic phase with variable composition. Magnetization measurements were collected for the solid solution and show complex magnetic ordering with competing ferromagnetic and antiferromagnetic interactions as the Sr content increases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal–Organic Framework for Ethylene Dimerization

The catalytic performance of a cobalt(II) single-site catalyst supported on the zirconia-like nodes of the metal organic–framework (MOF) NU-1000 is herein characterized by quantum chemical methods and compared to an iso-structural analogue incorporating nickel(II) as the active transition metal. The mechanisms of atomic layer deposition in MOFs and of catalysis are examined using density functional theory. We compare the catalytic activity of Co and Ni installed on the zirconia-like nodes for ethylene dimerization, considering three plausible pathways. We employ multiconfigurational wave function theory methods to further characterize the electronic structures of key transition states and intermediates. Finally, we report confirmation of Co catalytic activity for ethylene dimerization from experiments that were prompted by the computational prediction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

A Combined Variable-Temperature Neutron Diffraction and Thermogravimetric Analysis Study on a Promising Oxygen Electrode, SrCo 0.9 Nb 0.1 O 3–δ , for Reversible Solid Oxide Fuel Cells

The present study reported herein investigates the temperature–structure–stoichiometry relationship of a promising oxygen electrode SrCo 0.9 Nb 0.1 O 3-δ over a temperature (T) range from room temperature (RT) to 900 °C. The techniques employed are variable-temperature neutron diffraction (VTND) and thermogravimetric analysis (TGA). At $T$ < 75 °C, VTND reveals a tetragonal (P4/mmm) structure with a G-type magnetic ordering. Above 75 °C, the nucleus structure remains the same, while the magnetic ordering disappears. A phase transition from tetragonal ($P4/mmm$) to cubic ($Pm\overline3m$) is observed at 412 °C, where the two Co sites and three O sites in the $P4/mmm$ phase converge to one equivalent site, respectively. The phase transition temperature coincides with the peak temperature of oxygen uptake obtained by TGA. It is also observed that the Nb dopant has no preferred Co site to occupy. The oxygen vacancies are mostly located at the O3 site surrounding the Co2 site in the $P4/mmm$ structure. The intermediate-spin state of Co 3+ at the Co2 site is responsible for the observed distortions of CoO 6 octahedra, i.e., elongation of Co2O 6 octahedra and shortening of Co1O 6 octahedra along the c-axis, which is a phenomenon known as Jahn–Teller distortion. At high temperatures, large thermal displacement factor for O 2– is observed with high concentration of oxygen vacancies, providing a structural environment favorable to high O 2– conductivity in Nb-doped SrCoO 3 -based oxygen electrode materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Formal Oxidation States and Coordination Environments in the Catalytic Reduction of CO to Methanol

Fundamental insight into multi-electron, multi-proton redox reactions with organometallic catalysts is greatly facilitated by knowledge of the formal oxidation state of the metal center in each of the elementary reaction steps that comprise the catalytic cycle. X-ray absorption near edge structure (XANES) is utilized herein to quantify the oxidation states and coordination environment of the organometallic resting state and intermediates in a newly proposed catalytic reduction of carbon monoxide to methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗