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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Inverse Trans Influence and Uranium-Arene σ-Bonding Drive Molecular Geometry: Ligand Modification from Hard to Soft Flips the Oxide from Axial to Equatorial

A rare example of an equatorially bound terminal uranium(V) oxo complex in a chelating sulfur-based ligand environment, namely [(mes( Me,Ad ArS) 3 )U V (O eq )(THF)] (2), is presented. Octahedrally coordinated 2 is obtained by reaction of the mesitylene-anchored tris-thiophenolate-coordinated uranium(III) complex [U III ((SAr Ad,Me ) 3 mes)] (1) with the oxygen-atom transfer reagent N 2 O. The observed, equatorially bound oxo ligand in 2 is in stark contrast to its known tris-aryloxide analog, [(mes( Me,Ad ArO) 3 )U V (O ax )(THF)] (A), where the oxo ligand occupies the typically observed axial coordination site. Complexes 1 and 2 are characterized by single-crystal X-ray diffraction analyses and spectroscopic and magnetochemical methods, including 1 H NMR, UV/vis/NIR electronic absorption, as well as EPR spectroscopy and SQUID magnetometry, thus confirming the C S symmetry and the pentavalent oxidation state of 2. Encompassing quantum chemical calculations (DFT and CASPT2) on 2 and its tris-phenolate analog A, support and rationalize the structural and electronic differences. The molecular orbital pictures show that a stabilizing σ-bonding interaction arising from the U–O eq inverse trans influence (ITI) is present in 2 but missing in A. In 2, the sulfur 3p orbitals are closer in energy to the uranium 5f manifold than the arene π-system, leading to an ITI, while U–arene σ- or δ-bonding is not observed. Although the arene orbitals remain separated from the uranium 5f orbitals in A, the absence of an ITI allows the arene a 2u orbital to engage in a σ-type interaction with the metal. Thus, incorporating a tris-thiophenolate to an arene anchor introduces a new design concept in molecular f-element chemistry. This approach stabilizes an equatorially bound U(V) oxo center, contrasting with its tris-phenolate counterpart, where oxo coordination is axial. The observed geometric divergence, driven by competing ITI and U–arene interactions, not only tunes electronic structure but also leads to differentiated reactivity: only the phenolate analogs activate H 2 O, while the thiolates do not.

Hydrocarbons↗
DOE OSTI2025

Systematic Bandgap Engineering of a 2D Organic–Inorganic Chalcogenide Semiconductor via Ligand Modification

Hybrid organic–inorganic semiconductors present new opportunities for optoelectronic materials design not available in all-organic or all-inorganic materials. One example is silver phenylselenide (AgSePh) – or “mithrene” – a blue-emitting 2D organic–inorganic semiconductor exhibiting strong optical and electronic anisotropy. Here, we show that the bandgap of mithrene can be systematically tuned by introducing electron-donating and electron-withdrawing groups to the phenyl ligands. We synthesized nine mithrene variants, eight of which formed 2D van der Waals crystals analogous to those of AgSePh. Density functional theory calculations reveal that these 2D mithrene variants are direct-gap or nearly direct gap semiconductors. Furthermore, we identify correlations between the optical gap and three experimental observables – the Hammett constant, 77 Se chemical shift, and selenium partial charge – offering predictive power for bandgap tuning. These findings highlight new opportunities for applying the tools of chemical synthesis to semiconductor materials design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Systematic Catalyst Variation for Improved Stereoselective Epoxide Polymerization: Subtle Modifications Resulting in Superior Efficiency

Isotactic poly(propylene oxide) (iPPO) is a semicrystalline polyether that has emerged as a high-strength, photodegradable material for marine applications. To improve the accessibility of i PPO, catalysts with higher activity and selectivity are required. Using rational catalyst design informed by computational insights, we developed a flexibly tethered, bimetallic chromium catalyst exhibiting high enantioselectivity ( k rel ∼ 100) and unprecedented activity (TOF ∼ 50,000 h −1 ) for propylene oxide (PO) polymerization. Mechanistic studies reveal that high enantioselectivity originates from increased steric bulk at the ortho position of the salicylimine moiety, which increases steric repulsion between the alkoxide chain end and the ligand in the disfavored transition state. Furthermore, introducing geminal dimethyl groups that rigidify the flexible tether between the two ligand moieties significantly enhances catalyst activity by destabilizing the resting state during polymerization. The catalyst remains active at loadings as low as 0.5 ppm, enabling the synthesis of colorless, tough i PPO.

Ren, Bai-Hao [Cornell Univ., Ithaca, NY (United St↗
DOE OSTI2024

Exploring electron-beam induced modifications of materials with machine-learning assisted high temporal resolution electron microscopy

Directed atomic fabrication using an aberration-corrected scanning transmission electron microscope (STEM) opens new pathways for atomic engineering of functional materials. In this approach, the electron beam is used to actively alter the atomic structure through electron beam induced irradiation processes. One of the impediments that has limited widespread use thus far has been the ability to understand the fundamental mechanisms of atomic transformation pathways at high spatiotemporal resolution. Here, we develop a workflow for obtaining and analyzing high-speed spiral scan STEM data, up to 100 fps, to track the atomic fabrication process during nanopore milling in monolayer MoS 2 . An automated feedback-controlled electron beam positioning system combined with deep convolution neural network (DCNN) was used to decipher fast but low signal-to-noise datasets and classify time-resolved atom positions and nature of their evolving atomic defect configurations. Through this automated decoding, the initial atomic disordering and reordering processes leading to nanopore formation was able to be studied across various timescales. Using these experimental workflows a greater degree of speed and information can be extracted from small datasets without compromising spatial resolution. This approach can be adapted to other 2D materials systems to gain further insights into the defect formation necessary to inform future automated fabrication techniques utilizing the STEM electron beam.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Modification of Ni-20Cr corrosion dealloying behavior in molten fluorides via cold work induced plastic deformation

The corrosion dealloying behavior of cold-worked (CW) Ni20Cr alloy (wt%) was studied in molten LiF-NaF-KF (or FLiNaK) salts at 600 °C, equal to a homologous temperature (TH) of 0.52. Alloys were cold-rolled to achieve reductions of thickness of 10%, 30%, and 50% introducing plastic deformation and a high density of dislocations. Potentiostatic holds (Eapplied) were applied in two different electrode potential regimes. At 1.75VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, Cr dealloying to Cr(II) and Cr(III) is predominant, while at 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, both Ni and Cr are oxidized in molten FLiNaK at 600 °C. In these potential regimes, dealloyed Ni20Cr displayed bicontinuous porosity within the grain interior and at grain boundaries, driven by the high driving force for Cr dissolution and sustained by defect mediated outward solid state diffusion of Cr in parallel with surface diffusion of Ni. The bicontinuous porous structure developed was observed to undergo further coarsening and densification of the Ni-rich ligaments at a higher electrode potential. The main effect of CW observed is the introduction of plastic deformation and dislocation substructures that serve as short-circuit paths for Cr solid state diffusion to surfaces exposed to FLiNaK. This modified the evolution of the bicontinuous porous structure which increased with CW substantially. Kinetic analysis reveals that the Cr dealloying at +1.75 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ and 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ is initially charge transfer controlled, except for the 50% CW condition at 1.90 VK+/K$${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$, where the process becomes limited by slow Cr defect mediated bulk diffusion. The rate determining factors are explored and compared to experimental results.

Chan, Ho Lun↗
DOE OSTI2025

Global terrestrial nitrogen fixation and its modification by agriculture

Biological nitrogen fixation (BNF) is the largest natural source of new nitrogen (N) that supports terrestrial productivity, yet estimates of global terrestrial BNF remain highly uncertain. Here, in this study, we show that this uncertainty is partly because of sampling bias, as field BNF measurements in natural terrestrial ecosystems occur where N fixers are 17 times more prevalent than their mean abundances worldwide. To correct this bias, we develop new estimates of global terrestrial BNF by upscaling field BNF measurements using spatially explicit abundances of all major biogeochemical N-fixing niches. We find that natural biomes sustain lower BNF, 65 (52–77) Tg N yr −1 , than previous empirical bottom-up estimates, with most BNF occurring in tropical forests and drylands. We also find high agricultural BNF in croplands and cultivated pastures, 56 (54–58) Tg N yr −1 . Agricultural BNF has increased terrestrial BNF by 64% and total terrestrial N inputs from all sources by 60% over pre-industrial levels. Our results indicate that BNF may impose stronger constraints on the carbon sink in natural terrestrial biomes and represent a larger source of agricultural N than is generally considered in analyses of the global N cycle, with implications for proposed safe operating limits for N use.

Reis Ely, Carla R. [Oregon State Univ., Corvallis,↗
DOE OSTI2024

Study of graphene p-n junctions formed by the electrostatic modification of the SiO2 substrate

Abstract We study the transport properties of mm-scale CVD graphene p-n junctions, which are formed in a single gated graphene field effect transistor configuration. Here, an electrical-stressing-voltage technique served to modify the electrostatic potential in the SiO 2 /Si substrate and create the p-n junction. We examine the transport characteristics about the Dirac points that are localized in the perturbed and unperturbed regions in the graphene channel and note the quantitative differences in the Hall effect between the perturbed and unperturbed regions. The results also show that the longitudinal resistance is highly sensitive to the external magnetic field when the Hall bar device operates as a p-n junction.

Science & Technology - Other Topics↗
DOE OSTI2024

Inducing a tunable skyrmion-antiskyrmion system through ion beam modification of FeGe films

Abstract Skyrmions and antiskyrmions are nanoscale swirling textures of magnetic moments formed by chiral interactions between atomic spins in magnetic noncentrosymmetric materials and multilayer films with broken inversion symmetry. These quasiparticles are of interest for use as information carriers in next-generation, low-energy spintronic applications. To develop skyrmion-based memory and logic, we must understand skyrmion-defect interactions with two main goals—determining how skyrmions navigate intrinsic material defects and determining how to engineer disorder for optimal device operation. Here, we introduce a tunable means of creating a skyrmion-antiskyrmion system by engineering the disorder landscape in FeGe using ion irradiation. Specifically, we irradiate epitaxial B20-phase FeGe films with 2.8 MeV Au 4+ ions at varying fluences, inducing amorphous regions within the crystalline matrix. Using low-temperature electrical transport and magnetization measurements, we observe a strong topological Hall effect with a double-peak feature that serves as a signature of skyrmions and antiskyrmions. These results are a step towards the development of information storage devices that use skyrmions and antiskyrmions as storage bits, and our system may serve as a testbed for theoretically predicted phenomena in skyrmion-antiskyrmion crystals.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Metabolic Modification of Sphingobium lignivorans SYK-6 for Lignin Valorization Through the Discovery of an Unusual Transcriptional Repressor of Lignin-Derived Dimer Catabolism

Sphingobium lignivorans SYK-6 catabolizes guaiacylglycerol-..beta..-guaiacyl ether (GGE, a ..beta..-O-4-type dimer) and 1,2-diguaiacylpropane-1,3-diol (DGPD, a ..beta..-1-type dimer) derived from lignin. Recently, SLG_35860 containing TetR- and MarR-type transcriptional regulator motifs was suggested to be involved in the regulation of GGE and DGPD catabolism. Here we investigated the role of SLG_35860 in the transcriptional regulation of GGE and DGPD catabolism genes. SLG_35860 designated ligS repressed 11 genes involved in GGE and DGPD catabolism. LigS binds directly to specific sequences in the promoter region of each gene. The MarR domain was shown to be involved in these bindings; however, GGE, DGPD, and their metabolites did not function as effectors of LigS. We discovered unidentified compound(s) in the black liquor of oxygen-soda anthraquinone pulping of Japanese cedar that SYK-6 cannot metabolize and that acted as effector(s). Therefore, LigS constantly represses the transcription of the GGE and DGPD catabolism genes to low levels. Based on these findings, we examined the productivity of a polymer building block, 2-pyrone-4,6-dicarboxylic acid (PDC), from GGE, DGPD, and a GGE metabolite using an engineered ligS mutant. The rates of PDC production from each compound by this strain were 1.5-6.0 times higher than those of a PDC-producing strain carrying ligS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Chloride modification of vacuum-assisted blade-coated perovskite solar cells and mini-modules in ambient environment

Scalable deposition of perovskite thin films under ambient conditions remains a key challenge for the commercialization of perovskite photovoltaics, primarily due to the difficulty of controlling crystallization kinetics and suppressing non-radiative recombination during film formation. In this work, we present an effective strategy to modulate crystallization kinetics and non-radiative recombination in vacuum-quenched blade-coated perovskite films processed in air using chloride-based additives. By systematically comparing PbCl 2 and 3-chloropropylamine hydrochloride (Cl-PACl), we elucidate how different chloride incorporation pathways influence crystallization behavior and optoelectronic properties. In situ transmission and in situ photoluminescence measurements reveal that PbCl 2 acts as a transient additive that slows intermediate/perovskite phase formation while suppressing non-radiative recombination, leading to improved film quality. In contrast, Cl-PACl introduces additional trap states that deteriorate optoelectronic performance. As a result, PbCl 2 -modified perovskite solar cells achieve a champion power conversion efficiency (PCE) of 24.2% and remarkable operational stability, retaining over 90% of their initial performance after 800 hours of continuous illumination. Furthermore, we successfully scaled the process, fabricating a perovskite mini-module that delivered a champion efficiency of 18.0%. This study underscores the critical importance of coupling vacuum-assisted blade coating with transient additive engineering for achieving high-performance, stable, and scalable perovskite photovoltaics processed in ambient air.

14 SOLAR ENERGY↗
DOE OSTI2024

Photon-triggered jets as probes of multi-stage jet modification

Prompt photons are created in the early stages of heavy ion collisions and traverse the QGP medium without any interaction. Therefore, photontriggered jets can be used to study the jet quenching in the QGP medium. In this work, photon-triggered jets are studied through different jet and jet substructure observables for different collision systems and energies using the JETSCAPE framework. Since the multistage evolution used in the JETSCAPE framework is adequate to describe a wide range of experimental observables simultaneously using the same parameter tune, we use the same parameters tuned for jet and leading hadron studies. The same isolation criteria used in the experimental analysis are used to identify prompt photons for better comparison. For the first time, high-accuracy JETSCAPE results are compared with multi-energy LHC and RHIC measurements to better understand the deviations observed in prior studies. This study highlights the importance of multistage evolution for the simultaneous description of experimental observables through different collision systems and energies using a single parameter tune.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Deciphering yield modification of hadron-triggered semi-inclusive recoil jets in heavy-ion collisions

Jet quenching is recognized as critical evidence for the existence of the quark-gluon plasma (QGP) and serves as an essential probe to study its transport properties. Measurements of hadron-triggered semi-inclusive recoil jets have gained popularity due to its capability to probe jets over an extended phase space at low transverse momenta (p T ) and large radii. Recent ALICE measurements showed that the I AA , yield ratio of recoil jets between heavy-ion and p+p collisions, rises with jet p T and exceeds unity at high p T , contradicting conventional expectations that jet quenching should result in I AA values less than one. In this contribution, we re-examine the surface bias and study the effects of energy losses for both trigger hadrons and recoil jets on I AA , employing the Linear Boltzmann Transport (LBT) model to simulate jet-medium interactions. Our findings suggest that a large portion of hadrons used for the triggers undergoes substantial energy loss, despite surface bias. In particular, the energy loss of the trigger hadrons elevates the I AA baseline, corresponding to the case of no energy loss for recoil jets, to be greatly larger than unity. This enhancement of the baseline implies that the measured I AA values being larger than unity could still signal jet quenching.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Long-term relaxation of orientational disorder and structural modifications in molecular nitrogen at high pressure

Up to 17 GPa, the crystalline phases of N 2 are characterized by pronounced orientational disorder, whereas the higher-pressure phases of molecular N 2 are ordered. This raises the question about long-term relaxation of orientational disorder within the low- to intermediate-pressure regime. Here, in this study, this question is addressed by comparing synthetic with natural, chemically pure, solid N 2 that resides as inclusions in diamonds at 300 K for about 10 8 years at pressures up to 11 GPa. It is shown that disorder prevails at 8.7 GPa, 300 K, where both synthetic and natural N 2 assume the same structure. However, at 10.8 GPa, natural solid N 2 exhibits monoclinic distortion and partial orientational ordering of the molecules, both of which are not observed in synthetic material. This difference is interpreted as the result of long-term structural relaxation. The ordering mechanism is examined and placed into the context of the δ- to ε-N 2 transition. We present explanations for the absence of complete ordering of δ-N 2 .

Tschauner, Oliver↗
DOE OSTI2024

Pressure induced modification of electronic and magnetic properties of MnCrNbAl and MnCrTaAl

Spin-gapless semiconductor (SGS) is a new class of material that has been studied recently for potential applications in spintronics. This material behaves as an insulator for one spin channel, and as a gapless semiconductor for the opposite spin. In this work, we present results of a computational study of two quaternary Heusler alloys, MnCrNbAl and MnCrTaAl that have been recently reported to exhibit spin-gapless semiconducting electronic structure. In particular, using density functional calculations we analyze the effect of external pressure on electronic and magnetic properties of these compounds. It is shown that while these two alloys exhibit nearly SGS behavior at optimal lattice constants and at negative pressure (expansion), they are half-metals at equilibrium, and magnetic semiconductors at larger lattice constant. At the same time, reduction of the unit cell volume has a detrimental effect on electronic properties of these materials, by modifying the exchange splitting of their electronic structure and ultimately destroying their half-metallic/semiconducting behavior. Thus, our results indicate that both MnCrNbAl and MnCrTaAl may be attractive for practical device applications in spin-based electronics, but a potential compression of the unit cell volume (e.g. in thin-film applications) should be avoided.

Materials Science↗
DOE OSTI2026

Magnetic field induced modification of a first-order ferromagnetic transition in Eu 2 ⁢In

Here, we present a comprehensive study of the temperature-and magnetic-field-dependent magnetization, specific heat, and local crystal structure across the first-order ferromagnetic–paramagnetic transition in Eu 2 ⁢In. Anomalies in the magnetocaloric response are observed near 𝐻 ≈ 25 kOe, including changes in field scaling of magnetic entropy, local entropy exponent, and universal master curve, which suggest an apparent weakening of the first-order character of the transition. However, quantitative analysis of the magnetocaloric parameters together with modified Arrott plots demonstrates that the transition remains first order up to at least 70 kOe. Specific-heat measurements reveal a field-induced splitting of the sharp zero-field anomaly into a doublet, providing a natural explanation for the change in the magnetocaloric response. Magnetic-field-dependent extended x-ray absorption fine structure (EXAFS) measurements show no detectable field-induced changes in the local coordination environment of Eu. We therefore attribute these observations to a magnetic-field-induced two-step transition process in Eu 2 ⁢In.

Kumar, Ajay [Ames Laboratory (AMES), Ames, IA (Uni↗
DOE OSTI2024

Jet modification via 𝜋 0 -hadron correlations in Au + Au collisions at $\sqrt{s_{NN}}$ = 200 GeV

High-momentum two-particle correlations are a useful tool for studying jet-quenching effects in the quark-gluon plasma. Angular correlations between neutral-pion triggers and charged hadrons with transverse momenta in the range 4–12 GeV/𝑐 and 0.5–7 GeV/𝑐, respectively, have been measured by the PHENIX experiment in 2014 for Au + Au collisions at $\sqrt{s_{NN}}$ = 200 GeV. Suppression is observed in the yield of high-momentum jet fragments opposite the trigger particle, which indicates jet suppression stemming from in-medium partonic energy loss, while enhancement is observed for low-momentum particles. The ratio and differences between the yield in Au + Au collisions and 𝑝 + 𝑝 collisions, 𝐼 𝐴⁢𝐴 and Δ 𝐴⁢𝐴 , as a function of the trigger-hadron azimuthal separation, Δ⁢𝜙, are measured for the first time at the BNL Relativistic Heavy Ion Collider. Finally, these results better quantify how the yield of low-𝑝 𝑇 associated hadrons is enhanced at wide angle, which is crucial for studying energy loss as well as medium-response effects.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗