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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Improved Accuracy in Semi-Experimental Structure Determination by Resolving Problems Associated with Rotation of Principal Inertial Axes of Isotopologues: Structures of 1,3-Oxazole ( c -C 3 H 3 NO)

The rotational spectrum of the normal isotopologue of 1,3-oxazole (c-C 3 H 3 NO) was observed from 43 to 750 GHz. Over 3900 transitions for the ground vibrational state are measured, assigned, and least-squares fit to sextic centrifugally distorted-rotor Hamiltonians. The measured frequencies and resulting spectroscopic constants from this extended spectral range, combined with previous measurements of the nuclear quadrupole coupling constants, will facilitate astronomical searches for oxazole across the majority of the range of modern radiotelescopes. Spectra for a set of 30 oxazole isotopologues, which include multiple isotopic substitutions of each atom, are used to determine the first semi-experimental equilibrium ($r$$^{SE}_{e}$) structure and semi-experimental substitution structure ($r$$^{SE}_{e}$), each using CCSD(T) computed values for the vibration–rotation interaction and electron-mass corrections. The large number of isotopologues, including 21 isotopologues observed for the first time, and the redundant substitutions of each atom provide sufficient spectroscopic information to determine the $r$$^{SE}_{e}$ structure with the expected high level of accuracy and precision (0.0001 or 0.0002 Å in bond distances and 0.013 to 0.025° in bond angles). In the course of this study, we analyzed a known issue for some $r$$^{SE}_{e}$ structure determinations of near-oblate asymmetric tops in which inclusion of individual isotopologues degrades the structure determination. We demonstrate that this problem primarily arises from the difference in the values of the computed vibration–rotation interaction corrections as evaluated at the computed re geometry vs the $r$$^{SE}_{e}$ geometry of the “real” molecule. Our solution to this problem substantially improves the $r$$^{SE}_{e}$ structure of oxazole and likely can be generalized to many other molecules.

Chemical structure↗
DOE OSTI2023

Computational Screening of Supported Metal Oxide Nanoclusters for Methane Activation: Insights into Homolytic versus Heterolytic C–H Bond Dissociation

Since its discovery in zeolites, the [CuOCu] 2+ motif has played an important role in our understanding of selective methane activation over supported metal oxide nanoclusters. Although there are two known C-H bond dissoci-ation mechanisms, namely homolytic and heterolytic cleavage, most computational studies on optimizing metal oxide nanoclusters for improved methane activation reactivity have focused only on the homolytic mechanism. In this work, both mechanisms were examined for a set of 21 mixed metal oxide complexes of the form of [M 1 OM 2 ] 2+ (M 1 , M 2 = Mn, Fe, Co, Ni, Cu, Zn). Except for pure copper, heterolytic cleavage was found to be the dominant C-H bond activation pathway for all systems. Furthermore, mixed systems including [CuOMn] 2+ , [CuONi] 2+ , and [CuOZn] 2+ are predicted to possess similar methane activation activity as pure [CuOCu] 2+ . Furthermore, these results suggest that both homolytic and heterolytic mechanisms should be considered in computing methane activation energies on supported metal oxide nanoclusters.

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

Accessing Organonitrogen Compounds via C–N Coupling in Electrocatalytic CO 2 Reduction

Given the limited product variety of electrocatalytic CO 2 reduction reactions solely from CO 2 and H 2 O as the reactants, it is desirable to expand the product scope by introducing additional reactants that provide elemental diversity. The integration of inorganic heteroatom-containing reactants into electrocatalytic CO 2 reduction could in principle enable the sustainable synthesis of valuable products, such as organonitrogen compounds, which have widespread applications but typically rely on NH 3 derived from the energy-intensive and fossil-fuel-dependent Haber-Bosch process for their industrial scale production. Here, in this Perspective, research progress towards building C-N bonds in N-integrated electrocatalytic CO 2 reduction is highlighted, and the electrosyntheses of urea, acetamides, and amines are examined from the standpoint of reactivity, catalyst structure, and most fundamentally, mechanism. Mechanistic discussions of C-N coupling in these advances are emphasized and critically evaluated, with the aim of directing future investigations on improving the product yield and broadening the product scope of N-integrated electrocatalytic CO 2 reduction.

electrochemical reduction↗
DOE OSTI2023

Chemical Recycling of Thiol Epoxy Thermosets via Light-Driven C–C Bond Cleavage

Epoxy thermosets are high-volume materials that play a central role in a wide range of engineering applications; however, technologies to recycle these polymers remain rare. Here, we present a catalytic, light-driven method that enables chemical recycling of industrially relevant thiol epoxy thermosets to their original monomer at ambient temperature. This strategy relies on the proton-coupled electron transfer (PCET) activation of hydroxy groups within the polymer network to generate key alkoxy radicals that promote the fragmentation of the polymer through C–C bond β-scission. The method fully depolymerizes insoluble thiol epoxy thermosets into well-defined mixtures of small-molecule products, which can collectively be converted into the original monomer via a one-step dealkylation process. Notably, this process is selective and efficient even in the presence of other commodity plastics and additives commonly found in commercial applications. Finally, these results constitute an important step toward making epoxy thermosets recyclable and more generally exemplify the potential of PCET to offer a more sustainable end-of-life for a diverse array of commercial plastics.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mechanism of O 2 /NO-Promoted Oxidative C–C Bond Cleavage in Linear Alkanes

Selective oxidation of alkanes to oxygenated products remains a fundamental challenge, particularly if the goal is to promote C−C bond cleavage while minimizing formation of CO 2 . Oxidation conditions that use O 2 and nitrogen oxides (NO x ) have been shown to be very effective in promoting radical-mediated functionalization and oxidative carbon−carbon cleavage in saturated hydrocarbon polymers, such as polyethylene. Here, we investigate the mechanism of O 2 /NO-mediated oxidation of ndecane as a prototypical linear alkane substrate. These reactions enable identification and quantification of reactive intermediates, including nitrites, nitrates, alcohols, and ketones. Under the reaction conditions, these species convert into common ketone intermediates that evolve into α-diketones and other α-functionalized ketones, which undergo further conversion into carboxylic acids. Infrared (IR) spectroscopy indicates that HDPE oxidation proceeds through similar key intermediates. Together, these findings establish a mechanistic framework for NO x -mediated alkane oxidation and provide a foundation for the development of broadly applicable oxidative transformations.

Anions↗
DOE OSTI2021

High-performing commercial Fe–N–C cathode electrocatalyst for anion-exchange membrane fuel cells

Here, to reduce the cost of fuel cell stacks and systems, it is important to create commercial catalysts that are free of platinum group metals (PGMs). To do this, such catalysts must have very high activity, but also have the correct microstructure to facilitate the transport of reactants and products. Here, we show a high-performing commercial oxygen reduction catalyst that was specifically developed for operation in alkaline media and is demonstrated in the cathode of operating anion-exchange membrane fuel cells (AEMFCs). With H 2 /O 2 reacting gases, AEMFCs made with Fe–N–C cathodes achieved a peak power density exceeding 2 W cm –2 (>1 W cm –2 with H 2 /air) and operated with very good voltage durability for more than 150 h. These AEMFCs also realized an iR-corrected current density at 0.9 V of 100 mA cm –2 . Finally, in a second configuration, Fe–N–C cathodes paired with low-loading PtRu/C anodes (0.125 mg PtRu per cm 2 , 0.08 mg Pt per cm 2 ) demonstrated a specific power of 10.4 W per mg PGM (16.25 W per mg Pt).

25 ENERGY STORAGE↗
DOE OSTI2024

Integrating the PanDA Workload Management System with the Vera C. Rubin Observatory

The Vera C. Rubin Observatory will produce an unprecedented astronomical data set for studies of the deep and dynamic universe. Its Legacy Survey of Space and Time (LSST) will image the entire southern sky every three to four days and produce tens of petabytes of raw image data and associated calibration data over the course of the experiment’s run. More than 20 terabytes of data must be stored every night, and annual campaigns to reprocess the entire dataset since the beginning of the survey will be conducted over ten years. The Production and Distributed Analysis (PanDA) system was evaluated by the Rubin Observatory Data Management team and selected to serve the Observatory’s needs due to its demonstrated scalability and flexibility over the years, for its Directed Acyclic Graph (DAG) support, its support for multi-site processing, and its highly scalable complex workflows via the intelligent Data Delivery Service (iDDS). PanDA is also being evaluated for prompt processing where data must be processed within 60 seconds after image capture. This paper will briefly describe the Rubin Data Management system and its Data Facilities (DFs). Finally, it will describe in depth the work performed in order to integrate the PanDA system with the Rubin Observatory to be able to run the Rubin Science Pipelines using PanDA.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Direct functionalization of C-H bonds by electrophilic anions

Bond formation between two of the most inert molecules, alkanes and [B12X12]2- (X = Cl, Br), is performed in a two step process. Fragmentation of [B12X12]2- in the gas phase generates highly reactive [B12X11]- ions which spontaneously react with alkanes. The reaction mechanism was investigated using tandem mass spectrometry and gas-phase vibrational spectroscopy combined with electronic structure calculations. This effort revealed the unprecedented and counterintuitive electrophilic substitution of a proton in an alkane by a negatively charged ion resulting in a B-C bond formation. The product is a dianionic [B12X11CnH2n+1]2- species, in which H+ is electrostatically bound to the dianion. High flux ion soft-landing was performed to co-deposit [B12X11]- and complex organic molecules (phthalates) in thin layers on surfaces. Molecular structure analysis of the product films revealed that C-H functionalization by [B12X11]- occured in the presence of other more reactive functional groups. This observation demonstrates the utility of highly reactive fragment ions for defined bond formation processes and may pave the way to the use of gas phase ion chemistry for chemical synthesis in the condensed phase.

Warneke, Jonas↗
DOE OSTI2023

Second-Phase Hepatitis C Plasma Viral Kinetics Directly Reflects Reduced Intrahepatic Burden of Hepatitis C Virus

Mathematical models explain how antivirals control viral infections. Hepatitis C virus (HCV) treatment results in at least 2 phases of decline in viremia. Here, the first phase reflects clearance of rapidly produced virions. The second phase is hypothesized to derive from loss of infected cells but has been challenging to prove. Using single-cell methods, we quantified the number of hepatitis C virus (HCV)-infected hepatocytes in liver biopsies taken before and within 7 days of initiating direct-acting antivirals (DAAs) in a double-blinded randomized controlled trial testing 2 (sofosbuvir-velpatasvir) versus 3 (sofosbuvir-velpatasvir-voxilaprevir) DAAs. We employed thousands of intrahepatic measurements in 10 persons with chronic genotype 1a HCV infection: median proportion of infected hepatocytes declined from 11.3% (range, 1.3%–59%) to 0.6% (range, <0.3%–5.8%), a loss of 75%–95% infected hepatocytes. Plasma viremia correlated with numbers of HCV-infected hepatocytes (r = 0.77; P < .0001). Second-phase plasma dynamics and changes in infected hepatocytes were indistinct (P = .16), demonstrating that second-phase viral dynamics derive from loss of infected cells. DAAs led to a decline in intracellular HCV RNA and interferon-stimulated gene expression (P < .05 for both). We proved that second-phase viral dynamics reflect decay of intrahepatic burden of HCV, partly due to clearance of HCV RNA from hepatocytes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Calculation of the C 12 + C 12 sub-barrier fusion cross section in an imaginary-time-dependent mean field theory

The 12 C + 12 C sub-barrier fusion cross section is calculated within the framework of a time-dependent Hartree-Fock-based classical model using the Feynman path-integral method. The modified astrophysical S* factor is compared to direct and indirect experimental results. A good agreement with the direct data is found. In the lower-energy region where recent analyses of experimental data obtained with the Trojan horse method (THM) lead to contrasting results, the model predicts a nonresonant S* factor half-way between those results. Low-energy resonances revealed in the THM data are added to the calculation, and the relative reaction rate in the Gamow region is calculated. In particular, including 0 + resonances result in some agreement with the THM data. Here, the role of different resonances is discussed in detail, and their influence on the reaction rate at temperatures relevant to stellar evolution is investigated.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Effects of cluster correlations on fragment emission in 12 C+ 12 C at 50 MeV/nucleon

The effects of cluster correlations have been studied in the 12 C + 12 C reaction at 50 MeV/nucleon, using three AMD models, the AMD (AMD/D) without any additional cluster correlations, AMD/D-COALS with nucleon correlations based on a coalescence prescription for light cluster formations with A ≤ 4 and AMD-Cluster with an extended cluster correlation in two-nucleon collision processes and a special treatment for intermediate fragment formation with A ≤ 9. The angular distributions and energy spectra of fragments have been simulated and compared with the available experimental data. It is found that the cluster correlations take a crucial role to describe the productions of light charged particles (LCPs) and intermediate mass fragments (IMFs), and the AMD-cluster studied here provides a consistent overall reproduction of the experimental data. It is also shown that the significant effects of the secondary decay processes are involved for the fragment production besides the dynamical productions in the AMD stage. Detailed LCP and IMF production mechanisms involved in the intermediate energy heavy ion collisions are discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Charmonium χ c 0 and χ c 2 resonances in coupled-channel scattering from lattice QCD

In order to explore the spectrum of hidden-charm scalar and tensor resonances, we study meson-meson scattering with J P C = 0 + + , 2 + + in the charmonium energy region using lattice QCD. Employing a light-quark mass corresponding to m π ≈ 391 MeV , we determine coupled-channel scattering amplitudes up to around 4100 MeV considering all kinematically relevant channels consisting of a pair of open-charm mesons or a charmonium meson with a light meson. A single isolated scalar resonance near 4000 MeV is found with large couplings to D D ¯ , D s D ¯ s and the kinematically closed D * D ¯ * channel. A single tensor resonance at a similar mass couples strongly to D D ¯ , D D ¯ * and D * D ¯ * . We compare the extracted resonances to contemporary experimental candidate states, previous lattice results and theoretical modeling. In contrast to several other studies, we do not find any significant feature in the scalar amplitudes between the ground state χ c 0 ( 1 P ) and the resonance found around 4000 MeV. Published by the American Physical Society 2024

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity

A complex role for chlorine radicals Radicals are atoms or molecules that are highly reactive because they have an unpaired electron. A common means of investigating whether they are involved in a particular reaction is to try to trap them with an acceptor compound. Yang et al. reinvestigated a photoinduced alkane oxidation reaction for which a trapping study had previously implicated alkoxy radicals. Their spectroscopic, kinetic, and isotopic labeling studies revealed that chlorine, rather than alkoxy, was the key radical intermediate; the prior trapping results had stemmed from its complexation with alcohols. Science , abd8408, this issue p. 847

Science & Technology - Other Topics↗
DOE OSTI2021

Are 100 Ensemble Members Enough to Capture the Remote Atmospheric Response to +2°C Arctic Sea Ice Loss?

This study presents results from the Polar Amplification Multimodel Intercomparison Project (PAMIP) single-year time-slice experiments that aim to isolate the atmospheric response to Arctic sea ice loss at global warming levels of +2°C. Using two general circulation models (GCMs), the ensemble size is increased up to 300 ensemble members, beyond the recommended 100 members. After partitioning the response in groups of 100 ensemble members, the reproducibility of the results is evaluated, with a focus on the response of the midlatitude jet streams in the North Atlantic and North Pacific. Both atmosphere-only and coupled ocean–atmosphere PAMIP experiments are analyzed. Substantial differences in the midlatitude response are found among the different experiment subsets, suggesting that 100-member ensembles are still significantly influenced by internal variability, which can mislead conclusions. Despite an overall stronger response, the coupled ocean–atmosphere runs exhibit greater spread due to additional ENSO-related internal variability when the ocean is interactive. The lack of consistency in the response is true for anomalies that are statistically significant according to Student’s t and false discovery rate tests. This is problematic for the multimodel assessment of the response, as some of the spread may be attributed to different model sensitivities whereas it is due to internal variability. Here, we propose a method to overcome this consistency issue that allows for more robust conclusions when only 100 ensemble members are used.

58 GEOSCIENCES↗