Search NASA⌕ Search

SEARCH · Search NASA

Results for “Transfer reactions”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Shell-model calculations for two-neutron transfer near the $N=20$ island of inversion

We describe connections between shell-model calculation results and predictions for two-nucleon transfer reactions. Measurements of the 30 Mg(t,p) 32 Mg reaction were used to identify a low-lying shape-coexisting 0 + state in 32 Mg. Interpretations of those early, limited data were based on simple empirical models. The cross sections for two-nucleon transfer are, however, extremely sensitive to the details of the nuclear-structure. Motivated by the possibility of new high-resolution two-nucleon transfer measurements around the N = 20 Island of Inversion, we have performed shell-model calculations wave functions for states in the nuclei 30,32 Mg using the SDPF-M and SDPF-MU interactions, and from those calculations obtain the two-nucleon transfer amplitudes that we use to predict cross sections for the 28,30 Mg(t,p) 30,32 Mg reactions. The combined results show how the nuclear structure properties influence experimental observables for the (t,p) reaction. We compare our results with the existing data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Water Network Shape-Dependence of Local Interactions with the Microhydrated –NO 2 – and –CO 2 – Anionic Head Groups by Cold Ion Vibrational Spectroscopy

We report the structural evolutions of water networks and solvatochromic response of the CH 3 NO 2 – radical anion in the OH and CH stretching regions by analysis of the vibrational spectra displayed by cryogenically cooled CH 3 NO 2 – ·(H 2 O) n=1–6 clusters. The OH stretching bands evolve with a surprisingly large discontinuity at n = 6, which features the emergence of an intense, strongly red-shifted band along with a weaker feature that appears in the region assigned to a free OH fundamental. Very similar behavior is displayed by the perdeuterated carboxylate clusters, RCO 2 – ·(H 2 O) n=5–7 (R = CD 3 CD 2 ), indicating that this behavior is a general feature in the microhydration of the triatomic anionic domain and not associated with CH oscillators. Electronic structure calculations trace this behavior to the formation of a “book” isomer of the water hexamer that adopts a configuration in which one of the water molecules resides in an acceptor–acceptor–donor (AAD) (A = acceptor, D = donor) H-bonding site. Excitation of the bound OH in the AAD site explores the local network topology best suited to stabilize an incipient –XO 2 H–OH–(H 2 O) 2 intracluster proton-transfer reaction. These systems thus provide particularly clear examples where the network shape controls the potential energy landscape that governs water network-mediated, intracluster proton transfer. The CH stretching bands of the CH 3 NO 2 – ·(H 2 O) n=1–6 clusters also exhibit strong solvatochromic shifts, but in this case, they smoothly blue-shift with increasing hydration with no discontinuity at n = 6. Furthermore, this behavior is analyzed in the context of the solute-ion polarizability response and partial charge transfer to the water networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Spin assignments for $^{23}\hbox {Mg}$ levels and the astrophysical $^{22}\hbox {Na}(p,\gamma )^{23}\hbox {Mg}$ reaction

The 22 Na(p,γ) 23 Mg reaction is responsible for destruction of the long-lived radionuclide 22 Na produced during nova explosions. Since the reaction proceeds through resonances from levels in 23 Mg above the proton threshold at 7.581 MeV, the properties of these levels such as excitation energies, spins, and parities are crucial ingredients to deter- mine the 22 Na(p,γ) 23 Mg reaction rate. Despite recent studies of these levels, their spins are not well constrained in many cases. We have measured the 24 Mg(p,d) 23 Mg transfer reaction to determine spectroscopic properties of these levels at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory. The spin of the E x = 7.788 MeV level in 23 Mg is constrained to be J π = (3/2 + , 5/2 + ) through the present work. Here, the astrophysical 22 Na(p,γ) 23 Mg reaction rate at nova temperatures is updated accordingly. Nova nucleosynthesis model calculations using the newly updated 22 Na(p,γ) 23 Mg reaction rate shows that the final weighted abundance of the radionuclide 22 Na is increased by 42% compared to that obtained by using the previous 22 Na(p,γ) 23 Mg reaction rate of Sallaska et al. for a 1.35 M ⊙ ONeMg white dwarf.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Electrochemical Characterization of Dissolved Oxides in Molten FLiNaK

Molten fluoride salts have long been the subject of investigation given their application in a variety of industrial processes. Oxides are a common exogeneous impurity within these systems, and can lead to many operational and regulatory concerns. In recent studies, the electro-oxidation of dissolved metallic oxides has been attributed to a single step oxygen evolution reaction despite voltametric evidence suggesting otherwise. Here, we first use square wave voltammetry to confirm that the oxidation of dissolved oxides in fluorides proceeds via a two-electron transfer reaction and then demonstrate that the presence of a peroxide-mediated redox reaction better explains the electrochemical data. Numerical simulations were then used to support the determination of improved diffusion coefficients to enable electroanalytical measurements of the oxide concentration across at a variety of temperatures. A linear Arrhenius relationship was observed when the experimental data was corrected for ohmic resistance effects. Concentration measurements using the corrected square wave voltammetry data demonstrated high accuracy across a large range of concentrations, while the uncorrected data showed plateauing and high errors. In total, this work serves to rectify previously misconstrued electrochemical data of oxides in molten salts and demonstrate how accurate, in situ concentration measurements can be achieved in real-world systems.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Quantum physics of stars

Stars are slowly developing objects; the lifetimes of the different burning phases are determined by the strength of nuclear reactions, which in turn are defined by the quantum structure of the associated nuclei at the threshold and the respective reaction mechanisms. Stars, from the nuclear physics perspective, are cold environments where only a few of the key nuclear reactions have been measured at the actual stellar plasma temperatures. This is also the case for more dynamic astrophysical phenomena from the big bang to stellar explosions. Most of the nuclear reaction rates are therefore based on theoretical extrapolations. A number of discrepancies between these predictions and the associated stellar signatures have been observed, and many may be due to low-energy or near-threshold quantum effects. These effects need to be understood in order to reliably model nuclear reaction processes, not only for stars but also for low-temperature plasma environments such as controlled magnetic or inertial confinement fusion systems, which operate in similar temperature regimes. This review summarizes the various theoretical techniques presently used for deriving reaction rates and discusses possible quantum effects that may impact the reaction cross section near the reaction threshold. These resemble enhanced single-particle and cluster structures near threshold and associated interference effects. New experimental techniques such as deep-underground accelerators or the study of transfer reactions to mimic the quantum-mechanical transition strength, the so-called Trojan horse method, provide ways to directly or indirectly probe the reaction features that determine the reaction rates at stellar energies. Furthermore, this is demonstrated on a number of key nuclear reactions for different nucleosynthesis environments. Finally, current inconsistencies between experimental predictions and observations are discussed.

Models & methods for nuclear reactions↗
DOE OSTI2022

Impedance Modeling for Mixed Conductors with Simultaneous Insertion & Electrocatalytic Reactions: A Case Study of Transition-Metal Hydroxides in Aqueous Electrolyte

Electrochemical impedance spectroscopy (EIS) is commonly used to investigate the kinetics of mixed ionic–electronic conductor (MIEC) electrodes. Across various applications, MIECs exhibit ionic (e.g., insertion) and/or electronic (e.g., electrocatalytic) charge transfer reactions at the electrode/electrolyte interface. Bulk storage and transport of charge carriers also couple with these interfacial reactions. Here, we build a generalized, physics-based impedance model for MIECs with an ion-blocking current collector and explore how bulk and interfacial resistance, chemical capacitance, and DC polarization affect the impedance response. Using transition metal hydroxides as a case study, we provide guidance on extracting reaction kinetics or bulk resistance from the Nyquist plots in interface- or bulk-controlled conditions, respectively. Generalizing our EIS analysis enables a robust analysis of MIEC kinetics for a diverse set of systems.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Enzymatic Nitrogen Incorporation Using Hydroxylamine

Hydroxylamine-derived reagents have enabled versatile nitrene transfer reactions for introducing nitrogen-containing functionalities in small-molecule catalysis as well as biocatalysis. These reagents, however, result in poor atom economy and stoichiometric organic waste. Activating hydroxylamine (NH 2 OH) for nitrene transfer offers a low-cost and sustainable route to amine synthesis, since water is the sole byproduct. Despite its presence in nature, however, hydroxylamine is not known to be used for enzymatic nitrogen incorporation in biosynthesis. Here, we report an engineered heme enzyme that can utilize hydroxylammonium chloride, an inexpensive commodity chemical, for nitrene transfer. Directed evolution of Pyrobaculum arsenaticum protoglobin generated efficient enzymes for benzylic C–H primary amination and styrene aminohydroxylation. Mechanistic studies supported a stepwise radical pathway involving rate-limiting hydrogen atom transfer. Furthermore, this unprecedented activity is a useful addition to the ‘nitrene transferase’ repertoire and hints at possible future discovery of natural enzymes that use hydroxylamine for amination chemistry.

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

Investigating nuclei produced in 9 Li + 11 B reaction

In this contribution, a preliminary analysis of the first part of the experiment S2012 conducted at the ISAC-II facility of Canada’s particle accelerator center TRIUMF in Vancouver will be presented. The experiment aims to study highly clustered structures of nuclei created in multi-nucleon transfer reactions of 9 Li radioactive beam on natural boron target ( 11 B and 10 B). The main objective of the experiment is to study exotic structures created in neutron-rich 16 C nucleus in the range of higher excitation energies. The analysis presented here probes the existence of exotic cluster configurations and the quality of detected results using the invariant mass techniques.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Carbon Dioxide Insertion into Rhenium Hydrides as a Probe for the Impact of Solvent on Linear Free Energy Relationships between Thermodynamic and Kinetic Hydricity

The kinetics of CO 2 insertion into electronically different Re( R bpy)(CO) 3 H ( R bpy = 4,4'-R-2,2'- bipyridine; R = OMe, t Bu, Me, H, Br, COOMe, CF 3 ) complexes to form Re( R bpy)(CO) 3 {OC(H)O} compounds were determined in acetone, dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), and 3-methoxypropionitrile (3-MPN) and compared with previous data in acetonitrile (MeCN). The rates of CO 2 insertion for any one complex of the type Re(Rbpy)(CO) 3 H in different solvents correlates with the Dimroth-Reichardt (E T (30)) solvent parameter. Hammett plots in each solvent indicate that insertion reactions are faster for bpy ligands with electron-donating groups. There is, however, no correlation between the slope of the Hammett plot in different solvents and any common solvent parameter. Similarly, the enthalpies and entropies of activation and kinetic isotope effects associated with CO 2 insertion into Re(bpy)(CO) 3 H in different solvents do not correlate with any common solvent parameters. Theoretical calculations were used to determine the relative thermodynamic hydricities of Re( R bpy)(CO) 3 H type complexes in MeCN, acetone, DMF, and DMSO and in each solvent complexes with more electron-donating substituents on the bpy ligand are stronger hydride donors. Linear Free Energy Relationships (LFERs) between calculated thermodynamic and experimental kinetic hydricity, as measured through CO 2 insertion reactions, were observed in MeCN, acetone, DMF, and DMSO. Furthermore, the slopes of the LFERs correlate with the dielectric constant of the solvent. Overall, this work provides fundamental information about the thermodynamics and kinetics of hydride transfer reactions in different solvents, which is valuable for catalyst design.

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

Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer

It is well known that the solvent plays a critical role in ultrafast electron-transfer reactions. However, solvent reorganization occurs on multiple length scales, and selectively measuring short-range solute–solvent interactions at the atomic level with femtosecond time resolution remains a challenge. Here we report femtosecond X-ray scattering and emission measurements following photoinduced charge-transfer excitation in a mixed-valence bimetallic (Fe ii Ru iii ) complex in water, and their interpretation using non-equilibrium molecular dynamics simulations. Combined experimental and computational analysis reveals that the charge-transfer excited state has a lifetime of 62 fs and that coherent translational motions of the first solvation shell are coupled to the back electron transfer. Overall, our molecular dynamics simulations identify that the observed coherent translational motions arise from hydrogen bonding changes between the solute and nearby water molecules upon photoexcitation, and have an amplitude of tenths of ångströms, 120–200 cm -1 frequency and ~100 fs relaxation time. This study provides an atomistic view of coherent solvent reorganization mediating ultrafast intramolecular electron transfer.

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

Pre-steady-state kinetics of nanocrystal:molybdenum nitrogenase biohybrids reveals hole-scavenging efficiency is critical to N 2 reduction

Molybdenum (Mo) nitrogenase is a two-component enzyme complex that catalyzes the reduction of dinitrogen to ammonia and protons to hydrogen gas. We have shown that electrons for dinitrogen reduction can be delivered photochemically to the catalytic MoFe protein component by cadmium sulfide (CdS) nanocrystals. In this study, we used electron paramagnetic resonance spectroscopy to measure the transient populations of catalytic intermediates. We fit the populations with a pre-steady-state kinetic model, which allowed us to distinguish between productive and non-productive reaction pathways and extract the rate constants for the reaction. Our results demonstrated that the rate of catalytic electron delivery into MoFe protein increased with the concentration of the sacrificial electron donor. This enabled electron delivery to exceed the rate of hydride protonation, a relaxation pathway that competes with N 2 binding. Thus, managing the balance between electron transfer and hole transfer reactions is required to achieve a kinetic regime that favors N 2 reduction.

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

Kinetic Model of Photochemical Nitrogen Reduction [SWR-25-97]

The code in this repository was used to model the kinetics of photochemical nitrogen reduction. Each directory represents a manuscript. The directory titled Dahl_CRPS_2025 contains the code used to fit the kinetic models presented in the manuscript titled, "Pre-steady-state kinetics of nanocrystal:molybdenum nitrogenase biohybrids reveals hole-scavenging efficiency is critical to achieving N2 reduction" by Peter J. Dahl, Lauren M. Pellows, Zhi-Yong Yang, Lance C. Seefeldt, John W. Peters, Gordana Dukovic, David W. Mulder, and Paul W. King. Molybdenum (Mo) nitrogenase is a two-component enzyme complex that catalyzes the reduction of dinitrogen to ammonia and protons to hydrogen gas. We have shown that electrons for dinitrogen reduction can be delivered photochemically to the catalytic MoFe protein component by CdS nanocrystals. In this study, we used electron paramagnetic resonance spectroscopy to measure the transient populations of catalytic intermediates. We fit the populations with a pre-steady-state kinetic model which allowed us to distinguish between productive and non-productive reaction pathways and extract the rate constants for the reaction. Our results demonstrated that the rate of catalytic electron delivery into MoFe protein increased with the concentration of sacrificial electron donor. This enabled electron delivery to exceed the rate of hydride protonation, a relaxation pathway which competes with N2 binding. Thus, managing the balance between electron transfer and hole transfer reactions is required to achieve a kinetic regime that favors N2 reduction.

Dahl, Peter [National Renewable Energy Laboratory ↗
DOE OSTI2021

Persistent Homology Metrics Reveal Quantum Fluctuations and Reactive Atoms in Path Integral Dynamics

Nuclear quantum effects (NQEs) are known to impact a number of features associated with chemical reactivity and physicochemical properties, particularly for light atoms and at low temperatures. In the imaginary time path integral formalism, each atom is mapped onto a “ring polymer” whose spread is related to the quantum mechanical uncertainty in the particle’s position, i.e., its thermal wavelength. A number of metrics have previously been used to investigate and characterize this spread and explain effects arising from quantum delocalization, zero-point energy, and tunneling. Many of these shape metrics consider just the instantaneous structure of the ring polymers. However, given the significant interest in methods such as centroid molecular dynamics and ring polymer molecular dynamics that link the molecular dynamics of these ring polymers to real time properties, there exists significant opportunity to exploit metrics that also allow for the study of the fluctuations of the atom delocalization in time. Here we consider the ring polymer delocalization from the perspective of computational topology, specifically persistent homology, which describes the 3-dimensional arrangement of point cloud data, (i.e. atomic positions). We employ the Betti sequence probability distribution to define the ensemble of shapes adopted by the ring polymer. The Wasserstein distances of Betti sequences adjacent in time are used to characterize fluctuations in shape, where the Fourier transform and associated principal components provides added information differentiating atoms with different NQEs based on their dynamic properties. We demonstrate this methodology on two representative systems, a glassy system consisting of two atom types with dramatically different de Broglie thermal wavelengths, and ab initio molecular dynamics simulation of an aqueous 4 M HCl solution where the H-atoms are differentiated based on their participation in proton transfer reactions.

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

Electronic and Vibrational Coherence in Heterogeneous Electron Transfer (Final Report)

Interfacial electron transfer reactions constitute key physical phenomena central to a variety of energy related transport and conversion processes such as catalysis, photocatalysis, photovoltaics, energy storage, molecular electronics, etc. Heterogeneous material systems like organic/inorganic interfaces are of particular interest because they provide great potential to tailor properties according to application specific requirements. While electron transfer dynamics has been studied intensively in heterogeneous systems many questions remain unanswered. The significance of electronic-vibrational coupling and coherence is one aspect that has yet to be fully explored. The objective of this project is to develop and implement new ultrafast spectroscopic techniques based on pump four-wave mixing spectroscopy (pump-FWM) for studying the dynamics of vibrational coupling and coherence in heterogeneous electron transfer (HET) at molecule/semiconductor interfaces. The implementation of the spectroscopic setup allows to explore different four-wave mixing techniques and thus to identify a suitable approach to study the significance of vibrational as well as electronic coherence in HET.

14 SOLAR ENERGY↗
DOE OSTI2025

Study of alpha-resonances in ¹¹B via the ⁷Li(⁷Li, t ) reaction

The near-threshold proton resonance in ¹¹B, recently identified and characterized through independent experi-ments, plays a crucial role in understanding the unexpectedly high decay branch observed in the β-delayed proton emission (β− p) from the neutron halo nucleus ¹¹Be. Critical to interpreting this process is the determination of whether or not this state has any significant α-decay width (rα). A coincidence measurement was conducted to study the alpha-transfer reaction ⁷Li(⁷Li, t ) ¹¹B∗ → ⁷Li +α employing the Super-Enge Split Pole Spectrograph coupled with a silicon detector at Florida State University. This experiment aimed to investigate the structure of α resonances in ¹¹B in the Eₑₓ = 9.0 MeV–14 MeV energy region. In particular, to explore and constrain the α-decay branch of the near-threshold proton resonance at Eₑₓ = 11.44 MeV. No significant α-decay strength was observed from this state. Additionally, the experimental results provided insights into the state at Eₑₓ = 12.55 MeV, previously proposed as the T = 3/2 isobaric analog state of the ¹¹Be ground state. The observed decay pattern, dominated by α + ⁷Li, suggests a strong T = 1/2 component, indicating the need for further experimental measurements.

Lopez-Saavedra, E.↗
DOE OSTI2020

Effect of Molecular Structure of Quinones and Carbon Electrode Surfaces on the Interfacial Electron Transfer Process

Quinones can undergo thermodynamically reversible proton-coupled electron transfer reactions and are being applied as electroactive compounds in aqueous organic batteries. However, the electrochemical reversibility of these compounds is affected not only by their molecular structure but also by the properties of a carbon-based electrode surface. This study combines experimental and theoretical approaches to understand this dependence. Specifically, we study the electron transfer kinetics of two synthesized quinone derivatives and two commercially available ones with a glassy carbon, a highly ordered pyrolytic graphite, and a high-edge-density graphite electrode (HEDGE). The electrochemical reversibility is notably improved on the HEDGE, which shows a higher density of defects and presents oxygenated functional groups at its surface. The electron transfer kinetics are controlled by adsorbed species onto the HEDGE. Molecular dynamics simulation and quantum mechanics calculations suggest defects with oxygen-containing functional groups, such as C-O and C$=$O, on HEDGE surfaces drive the interaction with the functional groups of the molecules, during physisorption from van der Waals forces. The presence of sulfonic acid side groups and a greater number of aromatic rings in the molecular structure may contribute to a higher stabilization of quinone derivatives on HEDGEs. We propose that high-performance carbon-based electrodes can be obtained without catalysts for organic batteries, by the engineering of carbon-based surfaces with edge-like defects and oxygenated functional groups.

25 ENERGY STORAGE↗
DOE OSTI2023

Characterizing the multi-dimensional reaction dynamics of dihalomethanes using XUV-induced Coulomb explosion imaging

Site-selective probing of iodine 4d orbitals at 13.1 nm was used to characterize the photolysis of CH 2 I 2 and CH 2 BrI initiated at 202.5 nm. Time-dependent fragment ion momenta were recorded using Coulomb explosion imaging mass spectrometry and used to determine the structural dynamics of the dissociating molecules. Correlations between these fragment momenta, as well as the onset times of electron transfer reactions between them, indicate that each molecule can undergo neutral three-body photolysis. For CH 2 I 2 , the structural evolution of the neutral molecule was simultaneously characterized along the C–I and I–C–I coordinates, demonstrating the sensitivity of these measurements to nuclear motion along multiple degrees of freedom.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Thermodynamic and kinetic hydricity of transition metal hydrides

The prevalence of transition metal-mediated hydride transfer reactions in chemical synthesis, catalysis, and biology has inspired the development of methods for characterizing the reactivity of transition metal hydride complexes. Thermodynamic hydricity represents the free energy required for heterolytic cleavage of the metal–hydride bond to release a free hydride ion, H - , as determined through equilibrium measurements and thermochemical cycles. Kinetic hydricity represents the rate of hydride transfer from one species to another, as measured through kinetic analysis. This tutorial review describes the common methods for experimental and computational determination of thermodynamic and kinetic hydricity, including advice on best practices and precautions to help avoid pitfalls. The influence of solvation on hydricity is emphasized, including opportunities and challenges arising from comparisons across several different solvents. Connections between thermodynamic and kinetic hydricity are discussed, and opportunities for utilizing these connections to rationally improve catalytic processes involving hydride transfer are highlighted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗