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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Vibrational Signatures of Unrealized Phosphorus Suboxide Intermediates in White Phosphorus Oxidation Reactions

White phosphorus ignition notoriously produces the phosphoric acid anhydride P 4 O 10 , yet the intermediate oxidation steps remain undetermined. Here, we report the first geometric and vibrational characterization of two P 4 O 2 isomers, P 3 OPO and P 3 PO 2 , and substantiate a previously proposed cyclic P 4 O 2 isomer. We formally assign the infrared bands observed by Andrews and Mielke at 898 and 891 cm −1 to the antisymmetric P− O−P vibrations of P 3 OPO species. Additional bands corresponding to terminal P=O and −PO 2 stretches of P 3 OPO and P 3 PO 2 discussed herein also went unrecognized due to the peculiar bonding of P 4 O 2 species compared to oxo-bridged P 4 O x (x = 3−6) species. Sequential addition of oxygen atoms to the P 4 tetrahedron appears to form P 3 OPO and P 3 PO 2 , while cyclic P 4 O 2 is formed from P 2 O dimerization. CCSD(T) geometries, CCSD(T) + MP2[δVPT2] fundamental frequencies, and enthalpies of formation extrapolated using focal-point analysis are reported. The predicted enthalpies of formation relative to tetrahedral P 4 plus 3 Σ g − O 2 for bent-P 3 OPO, extended-P 3 OPO, P 3 PO 2 , and cyclic-P 4 O 2 are −93, −88, −85, and −63 kcal mol −1 , respectively.

Molecular structure↗
DOE OSTI2026

Nanosecond Structure of Radical Pair Intermediates from High-Frequency Quantum Oscillations: Insight into the Q A •– to Q B Electron Transfer Step in Purple Bacterial Photosynthesis

We demonstrate the validity of our approach to deduce, from the anisotropy of quantum oscillations, the geometry of short-lived radical pair intermediates in photosynthesis. A global fit of a two-dimensional W-band (94 GHz) electron paramagnetic resonance (EPR) experiment provides the same global minimum values for the geometry of the A-side radical pair P 700 •+ A 1A •− in photosystem I (PSI) as observed in a previous Q-band (34 GHz) EPR study, yet with a significantly increased convergence rate of 62%. This demonstrates that the global fit yields the correct radical pair geometry even at Q-band frequencies. With this information, we revisit our previous Q-band study of the cofactor arrangement of P 865 •+ Q A •− , the stabilized charge-separated state in purple bacterial reaction centers (RCs). Analysis of calculated two-dimensional data sets of P 865 •+ Q A •− reveals that the quantum oscillation technique is unaffected by a mirror ambiguity in disordered solids and thus can provide unambiguous solutions for all five Euler angles of the radical pair geometry. This enables us to elucidate the Q A •− to Q B electron transfer step in purple bacterial photosynthesis, the subject of controversial discussions for more than 25 years. Our results show that this electron transfer step involves a gating mechanism requiring a 60° rotation of the headgroup of Q A •− in its binding pocket.

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

Charge Tethering Drives Intermediate-Range Order and Slow Dynamics in Zwitterionic Liquids

We have synthesized and characterized a family of zwitterionic liquids (ZwLs) based on the poly(ethylene oxide) imidazolium cation and the alkyl sulfonate anion. To better rationalize ZwLs′ structural behavior and networkforming properties, we have computationally studied them in contrast to isostructural but chemically untethered ionic liquid (IL) analogues. Perhaps surprisingly, it is the molecular liquids and not the ILs that show the most selfassembly and intermediate-range order associated with scattering prepeaks; the ZwLs display also the slowest dynamics. This is consistent with prior work showing the importance of networks in considering the viscoelastic relaxation of liquids. We find that, because of their significantly large molecular dipoles, these zwitterions are versatile network-building blocks that result in highly viscous liquids. From a structural perspective, networks in these ZwLs sit somewhere in between what would be true chemical connectivity and the Coulombic networks observed in ionic liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Dynamic Activation of Single-Atom Catalysts by Reaction Intermediates: Conversion of Formic Acid on Rh/Fe 3 O 4 (001)

The stability and activity of supported single-atom catalysts (SACs) represent critical yet opposing factors limiting our ability to explore and exploit their unique properties. Here, this study demonstrates the operation of a switchable catalyst that is activated in the presence of surface intermediates and reverts back to a stable but inactive form when the reaction is completed. We employ atomically defined Rh-Fe 3 O 4 (001) catalysts to demonstrate how structurally stable Rh, bound in surface octahedral Fe sites, gets destabilized to form highly active Rh adatoms and small clusters. Conversion of formic acid, leading initially to surface formate and hydroxyl species, is employed as a model reaction to probe the dynamics of such processes. We find that surface hydroxyl recombination to water through the Mars van Krevelen mechanism reduces Rh coordination, triggering its conversion to active Rh adatoms. Since such lattice oxygen exchange is observed in many acid-base and redox chemistries, the process can be broadly applicable to controlling the activation of the range of SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Insights into Sustainable Nitrogen Fixation by Gas-phase Spectroscopic Measurements and Global Modeling of Reaction Intermediates in Humid Nitrogen Plasma

In this article, there is growing interest in reacting molecular nitrogen and water to sustainably synthesize fixed forms of nitrogen such as ammonia. In particular, low-temperature plasmas can activate these relatively inert feedstocks at or near room temperature without a catalyst. However, because of the enhanced reactivity and nonequilibrium chemistry, a diverse range of products is formed, and the underlying reaction mechanisms are exceedingly complex. In this work, we studied a simplified reactor consisting of a gaseous plasma containing controlled mixtures of nitrogen gas and water vapor. Densities of key chemical species such as N, H, OH, NH, and NO were measured by emission and laser-based spectroscopy as a function of the relative humidity. A global model was constructed and the reaction network was validated by comparing calculated species densities with experiments. We discover that N, a key initial intermediate for ammonia, strongly decreases in the presence of water vapor, and as a result, ammonia formation becomes limited at high relative humidity. This decrease is surprisingly not because N itself reacts, but because one of its main sources, an excited molecular nitrogen state, is reacted away. In addition, oxidation pathways for nitrogen, which lead to NO and related products, are found to be favored over reduction pathways because the corresponding reverse reactions are less significant. Together, this understanding helps explain previously reported observations of selectivity toward nitrogen oxides over ammonia, particularly at higher relative humidities.

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

Criegee Intermediates Compete Well with OH as a Cleaning Agent for Atmospheric Amides

Elucidating the chemical kinetics of stabilized Criegee intermediates (sCIs) in the atmosphere is critically important for climate modeling. Here, we report a class of very rapid bimolecular reactions of two sCIs, namely, CH 2 OO and syn-CH 3 CHOO, with amides. We used electronic structure calculations and kinetics calculations to elucidate a universal mechanism by which the oxygen atom of the carbonyl group in an amide is added to the carbon atom of the COO group in the sCI with simultaneous transfer of the amide hydrogen to the terminal oxygen atom of the carbonyl oxide of the sCI. The barriers for the mechanism are submerged below reactants by ∼9 kcal/mol, which means that the tight transition state is not the rate-determining step, and the rate constants are determined by loose free energy bottlenecks between the reactants and the precursor complexes. We calculate the rate constants due to these loose and barrierless transition states by variable-reaction-coordinate variational transition-state theory. We find that bimolecular reactions of sCIs with amides are very rapid, with rate constants 1 to 5 × 10 –10 cm 3 molecule –1 s –1 , which is a factor of 2 faster than the rate constants of carboxylic acids with sCIs and 10 2 faster than the rate constants of OH reactions with amides. This has the consequence that, under a wide range of conditions, sCIs are the major sink for atmospheric amides, in contrast to the usual assumption that OH radicals are the dominant sinks.

Amides↗
DOE OSTI2024

Neuromorphic intermediate representation: A unified instruction set for interoperable brain-inspired computing

Abstract Spiking neural networks and neuromorphic hardware platforms that simulate neuronal dynamics are getting wide attention and are being applied to many relevant problems using Machine Learning. Despite a well-established mathematical foundation for neural dynamics, there exists numerous software and hardware solutions and stacks whose variability makes it difficult to reproduce findings. Here, we establish a common reference frame for computations in digital neuromorphic systems, titled Neuromorphic Intermediate Representation (NIR). NIR defines a set of computational and composable model primitives as hybrid systems combining continuous-time dynamics and discrete events. By abstracting away assumptions around discretization and hardware constraints, NIR faithfully captures the computational model, while bridging differences between the evaluated implementation and the underlying mathematical formalism. NIR supports an unprecedented number of neuromorphic systems, which we demonstrate by reproducing three spiking neural network models of different complexity across 7 neuromorphic simulators and 4 digital hardware platforms. NIR decouples the development of neuromorphic hardware and software, enabling interoperability between platforms and improving accessibility to multiple neuromorphic technologies. We believe that NIR is a key next step in brain-inspired hardware-software co-evolution, enabling research towards the implementation of energy efficient computational principles of nervous systems. NIR is available atneuroir.org

Science & Technology - Other Topics↗
DOE OSTI2026

Can ferric-oxyl excited states explain elongated iron-oxygen bonds in heme peroxidase catalytic intermediates?

The use of X-ray structures to determine and interpret the ferryl iron-oxygen bond order in molecular oxygen-activating heme enzymes has, in the past, been controversial. This has mainly stemmed from the susceptibility of ferryl species to X-ray-induced electronic state changes. In this work we establishe using time-resolved serial femtosecond X-ray crystallography (tr-SFX) on a dye-decolourising peroxidase that the ferryl intermediate species (Compounds I and II) captured following in situ mixing of microcrystals with H 2 O 2 have single, rather than the double bond character expected. X-ray emission validated tr-SFX data with quantum refinement, time-dependent-DFT calculations and QM/MM geometry optimizations together support the concept that the single iron-oxygen bond character is not an indication of ferryl reduction or a protonated form (Fe IV -OH) but is instead attributed to the existence of accessible excited states possessing ferric-oxyl (Fe III –O •– ) character. Such states offer insight into the nature of ferryl heme.

Williams, Lewis J. [University of Essex, Colcheste↗
DOE OSTI2024

Revealing reaction intermediates in one-carbon elongation by thiamine diphosphate/CoA-dependent enzyme family

2-Hydroxyacyl-CoA lyase/synthase (HACL/S) is a thiamine diphosphate (ThDP)-dependent versatile enzyme originally discovered in the mammalian α-oxidation pathway. HACL/S natively cleaves 2-hydroxyacyl-CoAs and, in its reverse direction, condenses formyl-CoA with aldehydes or ketones. The one-carbon elongation biochemistry based on HACL/S has enabled the use of molecules derived from greenhouse gases as biomanufacturing feedstocks. We investigated several HACL/S family members with high activity in the condensation of formyl-CoA and aldehydes, and distinct chain-length specificities and kinetic parameters. Our analysis revealed the structures of enzymes in complex with acyl-CoA substrates and products, several covalent intermediates, bound ThDP and ADP, as well as the C-terminal active site region. One of these observed states corresponds to the intermediary α–carbanion with hydroxymethyl-CoA covalently attached to ThDP. This research distinguishes HACL/S from related sub-families and identifies key residues involved in substrate binding and catalysis. These findings expand our knowledge of acyloin-condensation biochemistry and offer attractive prospects for biocatalysis using carbon elongation.

2-hydroxyacyl-CoA lyase↗
DOE OSTI2025

Density functional theory-based surrogate kinetic models for heterogeneous reactions of hydrocarbon intermediates on silicon carbide

The increasing demand for high-performance materials in advanced technologies highlights the importance of achieving a fundamental understanding and potential control of silicon carbide (SiC) deposition processes. However, existing models often lack sufficient theoretical detail, relying heavily on empirical data and offering limited predictive capability. In particular, the complex surface chemistry governing SiC growth remains poorly understood. This study addresses these challenges by employing density functional theory (DFT) to investigate key heterogeneous reactions involving hydrocarbon intermediates on SiC surfaces, including dehydrogenation, hydrogenation, and carbon deposition. Transition state searches were conducted to identify reaction pathways and energy barriers. While first-principles calculations offer high accuracy, they are computationally intensive. To extend the utility of these first-principles results, vibrational analyses were performed using phonon-based statistical thermochemistry to compute temperature-dependent reaction rates which were used to develop Arrhenius-type surrogate kinetic models. Furthermore, the resulting framework provides a more rigorous, physically grounded basis for integrating atomistic insights into continuum-scale modeling, ultimately enabling improved prediction and optimization of SiC film growth in high-performance material systems.

Density Functional Theory↗
DOE OSTI2026

Intermediate time sub-diffusion and stress relaxation in ring polymer melts

The slow dynamics of non-concatenated ring melts remains a frontier problem in polymer science with implications for many soft material environments including cellular biophysics. Here, in this work, we report large-scale simulations of model ring melts that analyze the monomer and center-of-mass (CM) mean square displacements (MSD) and stress relaxation function on intermediate time and length scales. The degree of dynamical slowing down is characterized by the maximally sub-diffusive fractional time scaling exponents. The data span an exceptionally wide range of ring degrees of polymerization and stiffnesses and are not successfully organized based on the classic measure linear chain entanglement, N/N e . Rather, we find that the crossover degree of polymerization, N D , based on ring macromolecular caging that successfully allows master curves to be constructed for the long-time CM self-diffusion constant also collapses these temporal dynamic scaling exponents. Different properties display different exponents and exhibit one or two regimes of linear variation with the logarithm of N D / N . A distinct crossover of the CM-MSD and stress relaxation exponents emerges at sufficiently large N or stiffness that is not found for the monomer MSD, indicating a novel form of dynamic decoupling. This crossover aligns with the predicted critical degree of polymerization for transitioning from a weak to strong caging regime, indicative of activated transport. The latter may reflect the emergence of an intermolecular collective contribution to stress in analogy with dense soft colloidal matter. Suggestions are made for future theoretical work to address the rich patterns of behavior discovered.

Anomalous diffusion↗
DOE OSTI2026

Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. I. Conformer- and isomer-resolved infrared spectra

Transient carbon-centered hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation are characterized by infrared (IR) action spectroscopy under jet-cooled conditions with selective detection of hydroxyl (OH) radical products. Two distinct •QOOH isomers with radical sites at a primary carbon of one of the methyl groups (β-Me) or a secondary carbon (β-Et) of the ethyl group are identified by comparison with theoretically calculated IR absorption features for multiple conformers, including C–O, ethyl, and O–O torsions of the two isomers. Here, a master-equation analysis is developed and utilized to explore the conformational cooling process and the resultant conformer population distributions of the two isomers. Most of the IR features observed, including those in the strong fundamental and first overtone OH stretch regions as well as weaker combination bands involving OH stretch with torsion or OOH bend, are in good accord with computed anharmonic frequencies for the most populated conformers of the •QOOH_Et isomer. Relatively weak IR features most evident in the fundamental and first overtone OH stretch regions are ascribed to multiple conformers of the less stable •QOOH_Me isomer, along with a weak feature that is uniquely attributed to a combination band involving asymmetric CH 2 stretch and HCH bend of •QOOH_Me.

Chemical reaction jet spectroscopy↗
DOE OSTI2026

Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. II. Isomer-resolved unimolecular dynamics

Transient carbon-centered hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation are characterized by their time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) and cyclic ether products. Two distinct •QOOH isomers are examined with radical sites at a primary carbon of one of the methyl groups (β-Me) or a secondary carbon (β-Et) of the ethyl group. Energy-dependent unimolecular rates are obtained from the time-dependent appearance of OH products for the two isomers and compared with statistical microcanonical rates computed using RRKM theory, including heavy-atom tunneling, based on high-level theoretical calculations. A benchmark-corrected approach is utilized to compute high-accuracy stationary-point energies, most importantly, transition-state barriers, for the •QOOH_Me and •QOOH_Et isomers in isopentane oxidation, building on higher-level reference calculations for the oxidation of ethane (C 2 H 5 O 2 ) and propane (C 3 H 7 O 2 ), respectively. Here, the measured rates are compared with RRKM calculations incorporating the benchmark-corrected transition-state parameters, a vibrationally adiabatic multidimensional hindered-rotor treatment of key torsions, and quantum tunneling. Agreement between experiment and theory validates the statistical description and shows faster decay for •QOOH_Et due to its lower barrier. Both β-QOOH isomers decay almost exclusively to OH + cyclic ether products under the conditions studied.

Oxidation processes↗
DOE OSTI2024

First measurement in a magnetic confinement fusion experiment of the H 3 + H 3 → He 5 + n intermediate two-body resonant reaction

We report on the first experimental measurements made at a magnetic confinement fusion device of the tritium(T)-tritium(T) reaction T + T → He 4 + 2 n indicating the presence of the intermediate two-body resonant reaction T + T → He 5 + n . During the second deuterium-tritium campaign (DTE2) at the Joint European Torus, measurements of fusion plasmas with high tritium concentrations, n T / ( n T + n D ) ≈ 0.99 , heated with tritium neutral beam injection, were performed using the neutron time-of-flight (TOF) spectrometer TOFOR. We detect a peak in the neutron emission TOF spectrum consistent with the two-body resonant reaction. The TT neutron emission energy spectrum is modeled using an R -matrix framework where the distributions of the most likely model parameters given our experimental TOF data are determined utilizing a Markov chain Monte Carlo approach. We compare our best estimate of the T + T neutron emission energy spectrum with results obtained at inertial confinement fusion experiments at the OMEGA facility and find a spectral shape that is consistent with the energy dependency in the neutron spectrum observed at OMEGA. Published by the American Physical Society 2024

Physics↗
DOE OSTI2025

Hadronic vacuum polarization for the muon 𝑔 − 2 from lattice QCD: Complete short and intermediate windows

We present complete results for the hadronic vacuum polarization (HVP) contribution to the muon anomalous magnetic moment 𝑎 𝜇 in the short- and intermediate-distance window regions, which account for roughly 10% and 35% of the total HVP contribution to 𝑎 𝜇 , respectively. In particular, we perform lattice-QCD calculations for the isospin-symmetric connected and disconnected contributions, as well as corrections due to strong-isospin breaking. For the short-distance window observables, we investigate the so-called log-enhancement effects as well as the significant oscillations associated with staggered quarks in this region. For the dominant, isospin-symmetric light-quark-connected contribution, we obtain 𝑎$^{𝑙⁢𝑙,SD}_{𝜇⁡}$(conn) = 48.139⁢(11) stat ⁢(91) syst ⁢[92] total × 10 −10 and 𝑎$^{𝑙⁢𝑙,W}_{𝜇}$⁡(conn) = 206.90⁢(14) stat ⁢(61) syst ⁢[63] total × 10 −10 . We use Bayesian model averaging to fully estimate the covariance matrix between the individual contributions. Our determinations of the complete window contributions are 𝑎$^{SD}_{𝜇}$ = 69.05⁢(1) stat⁢ (21) syst ⁢[21] total × 10 −10 and 𝑎$^{W}_{𝜇}$ = 236.45⁢(17) stat⁢ (83) syst ⁢[85] total × 10 −10 . This work is part of our ongoing effort to compute all contributions to HVP with an overall uncertainty at the few-permille level.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Precision measurement of the longitudinal double-spin asymmetry for dijet production at intermediate pseudorapidity in polarized 𝑝⁢𝑝 collisions at $\sqrt{s}$ = 200 GeV

The STAR Collaboration reports precise measurements of the longitudinal double-spin asymmetry, 𝐴 𝐿⁢𝐿 , for dijet production with at least one jet at intermediate pseudorapidity 0.8 < 𝜂 jet < 1.8 in polarized proton-proton collisions at a center-of-mass energy of 200 GeV. This study explores partons scattered with a longitudinal momentum fraction (𝑥) from 0.01 to 0.5, which are predominantly characterized by interactions between high-𝑥 valence quarks and low-𝑥 gluons. The results are in good agreement with previous measurements at 200 GeV with improved precision and are found to be consistent with the predictions of global analyses that find the gluon polarization to be positive. In contrast, the negative gluon polarization solution from the JAM Collaboration is found to be strongly disfavored.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Leveraging intermediate resonances to probe CP violation at colliders

We explore the phenomenological impact of interference in tree-level contributions to three-body final states in $2\rightarrow 3$ scattering processes. This work introduces a novel search strategy leveraging asymmetries to enable sensitivity to CP-violating effects in less well-explored regions of phase space. Analytically, we demonstrate the effectiveness of this observable in probing interference between Standard Model charged-current decays and effective left-handed vector interactions, illustrated in a toy model featuring a scalar leptoquark, $S_1 \sim (3, 1, -\,1/3)$. Numerically, we apply this framework to studying the process $pp\rightarrow b \tau \nu $; unlike traditional high-$p_T$ searches or “bump hunts”, this approach utilizes an intermediate energy regime – where new physics is neither light enough to be produced on shell or heavy enough to justify an effective field theory treatment. A proof-of-principle analysis at parton level demonstrates a percent-level asymmetry, with sensitivity also to BSM weak-CP phase. While the specific phase sensitivity is diminished at particle level due to showering and detector effects, a machine learning classifier can recover sensitively to the presence of SM-BSM interference, significantly outperforming standard analysis methods. Notably discrimination between BSM signal and SM background could be achieved at the 2$\sigma $ level for the current LHC dataset and 8$\sigma $ at the High-Luminosity LHC. Moreover, this asymmetry observable as defined can also be more broadly applied to other searches for CP-violation in $2\rightarrow 3$ processes in present and future collider environments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗