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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Perspectives on the Dynamic Nuclear Polarization Mechanisms of Monoradicals: Overhauser Effect or Thermal Mixing?

This mini-review summarizes the evolving debate regarding the origins of the absorptive features seen in the dynamic nuclear polarization (DNP) spectra of certain monoradicals when they are irradiated at their electron Larmor frequency. This feature has drawn attention due to its reverse scaling with respect to the magnetic field strength and potential for high-field DNP. Two competing hypotheses have been introduced to explain the DNP feature based on (1) the Overhauser effect and low-temperature molecular dynamics and (2) radical clustering and a thermal mixing mechanism. Since the original discovery, a large number of experimental observations have been made in attempts to understand and ultimately leverage the mechanism. We summarize these observations and provide critical assessments of how the competing hypotheses approach them.

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

Performance Leap of Lithium Metal Batteries in LiPF 6 Carbonate Electrolyte by a Phosphorus Pentoxide Acid Scavenger

Phosphorus pentoxide (P 2 O 5 ) is investigated as an acid scavenger to remove the acidic impurities in a commercial lithium hexafluorophosphate (LiPF 6 ) carbonate electrolyte to improve the electrochemical properties of Li metal batteries. Nuclear magnetic resonance (NMR) measurements reveal the detailed reaction mechanisms of P 2 O 5 with the LiPF 6 electrolyte and its impurities, which removes hydrogen fluoride (HF) and difluor-ophosphoric acid (HPO 2 F 2 ) and produces phosphorus oxyfluoride (POF 3 ), OF 2 P-O-PF 5 - anions, and ethyl difluorophosphate (C 2 H 5 OPOF 2 ) as new electrolyte species. The P 2 O 5 -modified LiPF 6 electrolyte is chemically compatible with a Li metal anode and LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) cathode, generating a PO x F y -rich solid electrolyte interphase (SEI) that leads to highly reversible Li electrodeposition, while eliminating transition metal dissolution and cathode particle cracking. The excellent electrochemical properties of the P 2 O 5 -modified LiPF6 electrolytes are demonstrated on Li||NMC622 pouch cells with 0.4 Ah capacity, 50 mu m Li anode, 3 mAh cm -2 NMC622 cathode, and 3 g Ah -1 electrolyte/capacity ratio. The pouch cells can be galvanostatically cycled at C/3 for 230 cycles with 87.7% retention.

25 ENERGY STORAGE↗
DOE OSTI2023

Stabilization of a Heme-HNO Model Complex Using a Bulky Bis-Picket Fence Porphyrin and Reactivity Studies with NO

Nitroxyl, HNO/NO – , the one-electron reduced form of NO, is suggested to take part in distinct signaling pathways in mammals and is also a key intermediate in various heme-catalyzed NO x interconversions in the nitrogen cycle. Cytochrome P450nor (Cyt P450nor) is a heme-containing enzyme that performs NO reduction to N 2 O in fungal denitrification. The reactive intermediate in this enzyme, termed “Intermediate I”, is proposed to be an Fe-NHO/Fe-NHOH type species, but it is difficult to study its electronic structure and exact protonation state due to its instability. Here, we utilize a bulky bis-picket fence porphyrin to obtain the first stable heme-HNO model complex, [Fe(3,5-Me-BAFP)(MI)(NHO)], as a model for Intermediate I, and more generally HNO adducts of heme proteins. Due to the steric hindrance of the bis-picket fence porphyrin, [Fe(3,5-Me-BAFP)(MI)(NHO)] is stable (τ 1/2 = 56 min at -30 °C), can be isolated as a solid, and is available for thorough spectroscopic characterization. In particular, we were able to solve a conundrum in the literature and provide the first full vibrational characterization of a heme-HNO complex using IR and nuclear resonance vibrational spectroscopy (NRVS). Reactivity studies of [Fe(3,5-Me-BAFP)(MI)(NHO)] with NO gas show a 91 ± 10% yield for N 2 O formation, demonstrating that heme-HNO complexes are catalytically competent intermediates for NO reduction to N 2 O in Cyt P450nor. In conclusion, the implications of these results for the mechanism of Cyt P450nor are further discussed.

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

Stabilizing Ru-Formyl CO 2 Reduction Intermediates by Formation of Lewis Acid–Base Adducts: A Combined 2DIR and NMR Study

This work demonstrates how the stability of a Ru(II) formyl complex (cis-[Ru(bpy) 2 (CO)(CHO)][PF 6 ]), which is known to decarbonylate to form the metal hydride complex, is greatly enhanced by the addition of a Lewis acidic cation (Li + or Mg 2+ ). Multinuclear NMR is used to measure equilibrium constants of adduct formation, and then ultrafast 2DIR spectroscopy is applied to determine how the electronic structure and local molecular dynamics change upon complexation of the formyl ligand with the Lewis acid. We attribute the stabilization of the complex to the formation of a carbene-like structure where the bond strength between the Ru and the formyl group increases. The change in electronic structure is evidenced by steady-state NMR spectroscopy and DFT calculations. 2DIR measurements further confirm both the complexation of the formyl ligand with the Lewis acid and the change in electronic structure, where changes in vibrational frequency, relaxation kinetics, and a slowdown in the time scale of rotation about the metal-formyl bond are observed in the presence of Lewis acids.

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

Interplay between copper redox and transfer and support acidity and topology in low temperature NH 3 -SCR

Low-temperature standard NH 3 -SCR over copper-exchanged zeolite catalysts occurs on NH 3 -solvated Cu-ion active sites in a quasi-homogeneous manner. As key kinetically relevant reaction steps, the reaction intermediate Cu II (NH 3 ) 4 ion hydrolyzes to Cu II (OH)(NH 3 ) 3 ion to gain redox activity. The Cu II (OH)(NH 3 ) 3 ion also transfers between neighboring zeolite cages to form highly reactive reaction intermediates. Via operando electron paramagnetic resonance spectroscopy and SCR kinetic measurements and density functional theory calculations, we demonstrate here that such kinetically relevant steps become energetically more difficult with lower support Brønsted acid strength and density. Consequently, Cu/LTA displays lower Cu atomic efficiency than Cu/CHA and Cu/AEI, which can also be rationalized by considering differences in their support topology. By carrying out hydrothermal aging to eliminate support Brønsted acid sites, both Cu II (NH 3 ) 4 ion hydrolysis and Cu II (OH)(NH 3 ) 3 ion migration are hindered, leading to a marked decrease in Cu atomic efficiency for all catalysts.

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

Baryon–antibaryon photoproduction cross sections off the proton

The GlueX experiment at Jefferson Lab has observed 𝑝⁢$\overline{p}$ and, for the first time, Λ$\overlineΛ$ and 𝑝$\overlineΛ$ photoproduction from a proton target at photon energies up to 11.6 GeV. The angular distributions are forward peaked for all produced pairs, consistent with Regge-like 𝑡-channel exchange. Asymmetric wide-angle antibaryon distributions show the presence of additional processes. In a phenomenological model, we find consistency with a double-𝑡-channel exchange process where antibaryons are created only at the middle vertex. The model matches all observed distributions with a small number of free parameters. In the hyperon channels, we observe a clear distinction between photoproduction of the Λ$\overlineΛ$ and 𝑝$\overlineΛ$ systems but general similarity to the 𝑝$\overline{p}$ system. We report both total cross sections and cross sections differential with respect to momentum transfer and the invariant masses of the created particle pairs. No narrow resonant structures were found in these reaction channels. The suppression of 𝑠$\overline{s}$ quark pairs relative to 𝑑$\overline{d}$ quark pairs is similar to what has been seen in other reactions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Analysis of Σ* via isospin selective reaction 𝐾 𝐿 ⁢𝑝 →𝜋 + ⁢Σ 0

The isospin-selective reaction 𝐾 𝐿 ⁢𝑝 →𝜋 + ⁢Σ 0 provides a clean probe for investigating 𝐼 =1 Σ* resonances. In this work, we perform an analysis of this reaction using an effective Lagrangian approach for the first time, incorporating the well-established Σ⁡(1189)⁢1/2 + , Σ⁡(1385)⁢3/2 + , Σ⁡(1670)⁢3/2 − , and Σ⁡(1775)⁢5/2 − states, while also exploring contributions from other unestablished states. By fitting the available differential cross-section and recoil polarization data, adhering to partial-wave phase conventions same as the Particle Data Group, we find that besides the established resonances, contributions from Σ⁡(1660)⁢1/2 + , Σ⁡(1580)⁢3/2 − , and a Σ*⁢(1/2 − ) improve the description. Notably, a Σ*⁢(1/2 − ) resonance with mass around 1.54 GeV, consistent with Σ⁡(1620)⁢1/2 − , is found to be essential for describing the data in this channel, a stronger indication than found in previous analyses focusing on 𝜋⁢Λ final states. While providing complementary support for Σ⁡(1660)⁢1/2 + and Σ⁡(1580)⁢3/2 − , our results highlight the importance of the Σ⁡(1620)⁢1/2 − region in 𝐾 𝐿 ⁢𝑝 →𝜋 + ⁢Σ 0 . Future high-precision measurements are needed to solidify these findings and further constrain the Σ* spectrum.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Catalytic Resonance Theory: The Catalytic Mechanics of Programmable Ratchets

Catalytic reaction networks of multiple elementary steps operating under dynamic conditions via a programmed input oscillation are difficult to interpret and optimize due to reaction system complexity. To understand these dynamic systems, individual elementary catalytic reactions oscillating between catalyst states were evaluated to identify their three fundamental characteristics that define their ability to promote reactions away from equilibrium. First, elementary catalytic reactions exhibit directionality to promote reactions forward or backward from equilibrium as determined by a ratchet directionality metric comprised of the input oscillation duty cycle and the reaction rate constants. Second, catalytic ratchets are defined by the catalyst state of strong or weak binding that permit reactants to proceed through the transition state. Third, elementary catalytic ratchets exhibit a cutoff frequency which defines the transition in applied frequency for which the catalytic ratchet functions to promote chemistry away from equilibrium. All three ratchet characteristics are calculated from chemical reaction parameters including rate constants derived from linear scaling parameters, reaction conditions, and catalyst state. The characteristics of the reaction network’s constituent elementary catalytic reactions provided an interpretation of complex reaction networks and a method of predicting the behavior of dynamic surface chemistry on oscillating catalysts.

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

New constraints on the Al 25 ( p , γ ) reaction and its influence on the flux of cosmic γ rays from classical nova explosions

The astrophysical 25 Al(p,γ) 26 Si reaction represents one of the key remaining uncertainties in accurately modeling the abundance of radiogenic 26 Al ejected from classical novae. Specifically, the strengths of key proton-unbound resonances in 26 Si, that govern the rate of the 25 Al(p,γ) reaction under explosive astrophysical conditions, remain unsettled. Here, we present a detailed spectroscopy study of the 26 Si mirror nucleus 26 Mg. We have measured the lifetime of the 3 + , 6.125-MeV state in 26 Mg to be 19(3) fs and provide compelling evidence for the existence of a 1 – state in the T = 1, A = 26 system, indicating a previously unaccounted for ℓ = 1 resonance in the 25 Al(p,γ) reaction. Using the presently measured lifetime, together with the assumption that the likely 1 – state corresponds to a resonance in the 25 Al + p system at 435.7(53) keV, we find considerable differences in the 25 Al(p,γ) reaction rate compared to previous works. Furthermore, based on current nova models, we estimate that classical novae may be responsible for up to ≈ 15% of the observed galactic abundance of 26 Al.

20 ≤ A ≤ 38↗
DOE OSTI2023

New 26 P( p, γ ) 27 S Thermonuclear Reaction Rate and Its Astrophysical Implications in the rp -process

Accurate nuclear reaction rates for 26 P(p, γ) 27 S are pivotal for a comprehensive understanding of the rp-process nucleosynthesis path in the region of proton-rich sulfur and phosphorus isotopes. However, large uncertainties still exist in the current rate of 26 P(p, γ) 27 S because of the lack of nuclear mass and energy level structure information for 27 S. We reevaluate this reaction rate using the experimentally constrained 27 S mass, together with the shell model predicted level structure. It is found that the 26 P(p, γ) 27 S reaction rate is dominated by a direct capture reaction mechanism despite the presence of three resonances at E = 1.104, 1.597, and 1.777 MeV above the proton threshold in 27 S. The new rate is overall smaller than the other previous rates from the Hauser–Feshbach statistical model by at least 1 order of magnitude in the temperature range of X-ray burst interest. In addition, we consistently update the photodisintegration rate using the new 27 S mass. The influence of new rates of forward and reverse reaction in the abundances of isotopes produced in the rp-process is explored by postprocessing nucleosynthesis calculations. The final abundance ratio of 27 S/ 26 P obtained using the new rates is only 10% of that from the old rate. The abundance flow calculations show that the reaction path 26 P(p, γ) 27 S(β + ,ν) 27 P is not as important as previously thought for producing 27 P. The adoption of the new reaction rates for 26 P(p, γ) 27 S only reduces the final production of aluminum by 7.1% and has no discernible impact on the yield of other elements.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Plasmonic Hot-Carrier Generation and Catalysis in Ti 3 C 2 O 2 from Real-Time TDDFT Simulations

Photoinduced hot electrons are central to plasmon-driven catalysis. Atomically thin Ti 3 C 2 O 2 , with high carrier density and broad optical absorption, offers a promising platform for plasmon-driven reactions. However, comprehensive investigations of its plasmon resonance, hot-carrier generation, and plasmonic catalytic performance remain limited. In this work, real-time time-dependent density functional theory (rt-TDDFT) was employed to study Ti 3 C 2 O 2 ’s plasmon excitation and hot-carrier generation from nonradiative plasmon damping. The temporal evolution of the dipole moment reveals plasmon resonance in Ti 3 C 2 O 2 , followed by strong plasmon damping that redistributes the stored energy to generate hot carriers. Ti 3 C 2 O 2 with low oxygen vacancy concentration (O v -Ti 3 C 2 O 2 ) exhibits plasmonic behavior resembling the pristine surface, and the plasmon-generated hot electrons can markedly reduce the dissociation barrier of CO 2 at the oxygen vacancy. These findings provide fundamental insights into the plasmonic properties of Ti 3 C 2 O 2 and how they drive its catalytic performance in surface reactions, which is valuable for advancing plasmon-driven catalysis.

CO2 reduction↗
DOE OSTI2020

Single-Step Conversion of Ethanol to n-Butene over Ag-ZrO2/SiO2 Catalysts

Ethanol is a promising platform molecule for production of a variety of fuels and chemicals. Of particular interest is producing middle distillate fuels (i.e., jet and diesel blendstock) from renewable ethanol feedstock. State-of-the-art alcohol-to-jet technology requires multiple process steps based on catalytic dehydration of ethanol to form ethylene, followed by sometimes a multi-step oligomerization, and then hydrotreatment and distillation. Here we report on a new catalytic route in which ethanol is directly converted to n-butene (1- and 2-butene mixtures) over Ag-ZrO2/SBA-16, thus offering the potential for a reduction in the number of required processing steps versus conventional alcohol-to-jet technology. This catalyst system provides the balanced metal and Lewis acid sites required to selectively facilitate a cascading sequence of reactions that includes dehydrogenation, aldol condensation, Meerwein–Ponndorf–Verley reduction, dehydration, and hydrogenation. High conversion and selectivity toward either n-butene or 1,3-butadiene is achieved by tuning the hydrogen feed partial pressure and other process/catalyst parameters. With sufficient hydrogen partial pressure 1,3-butadiene is completely and selectively hydrogenated to form n-butene. The reaction mechanism was elucidated through operando-nuclear magnetic resonance investigations coupled with reactivity measurements. Combined experimental-computational investigation reveals how changes in silver and zirconium composition and the silver oxidation state affects reactivity under controlled hydrogen partial pressures and after prolonged run times. Finally, catalyst effectiveness also was demonstrated when using wet ethanol feed, thus highlighting process flexibility in terms of feedstock purity requirements. This work was financially supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, and was performed at the Pacific Northwest National Laboratory (PNNL) under Contract No. DE-AC05-76RL01830 and the National Renewable Energy Laboratory under Contract No. DE-AC36- 08GO28308. Part of the work conducted by S. A. Akhade was performed under the auspices of the U.S. DOE at Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344. This work was partly supported through the PNNL-WSU Distinguished Graduate Research Program for ADW. NMR and XPS experiments were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research

Dagle, Vanessa↗
DOE OSTI2022

Direct Measurement of Resonances in Be 7 ( α , γ ) C 11 Relevant to ν p -Process Nucleosynthesis

Here, we have performed the first direct measurement of two resonances of the 7 Be(α,γ) 11 C reaction with unknown strengths using an intense radioactive 7 Be beam and the DRAGON recoil separator. We report on the first measurement of the 1155 and 1110 keV resonance strengths of 1.73 ± 0.25(stat) ± 0.40(syst) eV and $125^{+27}_{-25}$(stat) ± 15(syst) meV, respectively. The present results have reduced the uncertainty in the 7 Be(α,γ) 11 C reaction rate to ~9.4%–10.7% over $\textit{T}$ = 1.5–3 GK, which is relevant for nucleosynthesis in the neutrino-driven outflows of core-collapse supernovae ($\textit{νp}$ process). We find no effect of the new, constrained reaction rate on $\textit{νp}$-process nucleosynthesis.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Coherent Reaction between Molecular and Atomic Bose-Einstein Condensates: Integrable Model

Here, we solve a model that describes a stimulated conversion between ultracold bosonic atoms and molecules. The reaction is triggered by a linearly time-dependent transition throughout the Feshbach resonance. Our solution predicts a dependence, with a dynamic phase transition, of the reaction efficiency on the transition rate for both atoms-to-molecule pairing and molecular dissociation processes. We find that for the latter process with a linear energy dispersion of atomic modes, the emerging phase can have a thermalized energy distribution of noninteracting bosons with the temperature defined by the rate of the transition. This provides a simple interpretation of the phase transition in terms of the creation of equilibrium Bose-Einstein condensate.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Lowest-energy broad 𝛼-cluster resonances in 19 F

There is strong astrophysical interest in the structure of 19 F states near the α-decay threshold, as their properties are important for understanding the development of α clustering in the 20 Ne region. The emergence of clustered states, and more generally of states that couple strongly to reaction channels near their decay thresholds, is also a topic of current interest in theoretical nuclear physics. In this work, we determine the parameters of broad low-spin states in 19 F near the α-decay threshold and present a theoretical study of these states. The analysis is restricted to ℓ = 0 and 1 resonances in the α + 15 N system close to the α threshold in 19 F. Excitation functions for 15 N(α,α) elastic scattering were measured using the Thick Target Inverse Kinematics (TTIK) method, and these new data, together with older high–energy-resolution measurements, were analyzed within the R-matrix framework. The nuclear structure of 19 F was calculated using configuration-interaction methods with a recently developed effective interaction Hamiltonian. As a result, we identify a sequence of α-cluster resonances in 19 F and map the distribution of clustering strength, which is relevant for astrophysical reaction modeling and for the theoretical understanding of many-body dynamics and the emergence of clustering in loosely bound or unstable nuclei. Furthermore, the work advances theoretical insight into the origins of clustering and highlights open questions for future theoretical and experimental studies.

19F↗
DOE OSTI2025

Benchmarking fast-neutron response of 7 Li-enriched C 7 LYC scintillators: Simulations and experiment

New insights into the fast neutron response of 7 Li-enriched C 7 LYC scintillators have been obtained through detailed Geant4 simulations of 35 Cl(n,p) and 35 Cl(n, α) reactions that are primarily responsible for the fast neutron response of C 7 LYC. The light output of a 1” x1” C 7 LYC detector was simulated using the Birks equation for light quenching in scintillators. The simulations were benchmarked against neutron scattering data from a 12 C target obtained with a white neutron beam at the Los Alamos LANSCE facility and fourteen 1”x1” C 7 LYC detectors. Incident neutron energies extracted from time-of-flight measurements, and appropriate recoil corrections for the different detector angles were used to map the response of C 7 LYC to mono-energetic neutrons. Resonances in the 35 Cl(n,p) reaction cross-section below 3 MeV incident neutron energy were directly observed in C 7 LYC. The experimental data and simulations are compared with ENDF databases, as well as recent direct cross-section measurements of neutrons scattered from a 35 Cl target. In conclusion, the results suggest a scrutiny of the 35 Cl(n,p) and 35 Cl(n, α) cross sections at low energy in the ENDF library.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗