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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Heterogeneous Reaction of ClONO2(g) + NaCl(s) to Cl2(g) + NaNO3(s)

The heterogeneous reaction of ClON02 + NaCl yields Cl2 + NaNO3 (eq 1) was investigated over a temperature range 220-300 K in a flow-tube reactor interfaced with a differentially pumped quadrupole mass spectrometer. Partial pressures of ClON02 in the range 10(exp -8) - 10(exp -5) Torr were used. Granule sizes and surface roughness of the NaCl substrates were determined by using a scanning electron microscope, and in separate experiments, surface areas of the substrates were measured by using BET analysis of gas-adsorption isotherms. For dry NaCl substrates, both the decay rates of ClON02 and the growth rates Of C12 were used to obtain reaction probabilities, gamma(sub l) = (4.6 +/- 3.0) x 10(exp -3) at 296 K and (6.7 +/- 3.2) x 10(exp -1) at 225 K, after considering the internal surface area, The error bars represent 1 standard deviation. The Cl2 yield based on the ClONO2 reacted was measured to be 1.0 +/- 0.2. In order to mimic the conditions encountered in the lower stratosphere, the effect of water vapor pressures between 5 x 10(exp -5) and 3 x 10(exp -4) Torr on reaction 1 was also studied. With added H20, reaction probabilities, gamma = (4.1 +/- 2.1) x 10(exp -3) at 296 K and (4.7 +/- 2.9) x 10(exp -3) at 225 K, were obtained. A trace of HOCl, the reaction product from the ClON02 + H20 yield HOCl + HN03 reaction, was observed in addition to the C12 product from reaction 1. The implications of this result for the enhancement of hydrogen chloride in the stratosphere after the El Chichon volcanic eruption and for the marine troposphere are discussed.

Timonen, Raimo S.↗
NASA NTRS1997

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

Hoobler, Ray J.↗
NASA NTRS1995

Heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(s)

The heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) (eq 1) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(S) (eq 2) were investigated over the temperature range 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. Either a chemical ionization mass spectrometer (CIMS) or an electron-impact ionization mass spectrometer (EIMS) was used to provide suitable detection sensitivity and selectivity. In order to mimic atmospheric conditions, partial pressures of HNO3 and N2O5 in the range 6 x 10(exp -8) - 2 x 10(exp -6) Torr were used. Granule sizes and surface roughness of the solid NaCl substrates were determined by using a scanning electron microscope. For dry NaCl substrates, decay rates of HNO3 were used to obtain gamma(1) = 0.013 +/- 0.004 (1sigma) at 296 K and > 0.008 at 223 K, respectively. The error quoted is the statistical error. After all corrections were made, the overall error, including systematic error, was estimated to be about a factor of 2. HCl was found to be the sole gas-phase product of reaction 1. The mechanism changed from heterogeneous reaction to predominantly physical adsorption when the reactor was cooled from 296 to 223 K. For reaction 2 using dry salts, gamma(2) was found to be less than 1.0 x 10(exp -4) at both 223 and 296 K. The gas-phase reaction product was identified as ClNO2 in previous studies using an infrared spectrometer. An enhancement in reaction probability was observed if water was not completely removed from salt surfaces, probably due to the reaction of N2O5(g) + H2O(s) yields 2HNO3(g). Our results are compared with previous literature values obtained using different experimental techniques and conditions. The implications of the present results for the enhancement of the hydrogen chloride column density in the lower stratosphere after the El Chichon volcanic eruption and for the chemistry of HCl and HNO3 in the marine troposphere are discussed.

Leu, Ming-Taun↗
NASA NTRS2000

Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

Thorn, R. Peyton, Jr.↗
NASA NTRS1996

Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition reactions of FORP compositions used in this study were unremarkable, Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant-system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid MMH and liquid NTO in a confined space. The test hardware was constructed with pressure- and temperature-measurement devices to determine if the expected fuel oxidizer reaction would result in increased energy release when FORP, FORP constituents, or propellant-system corrosion products were present. These tests demonstrated that FORP, MMHN, AN, or Inconel corrosion products can induce a mixture of MMH and NTO to produce component-damaging energies. The simulation-test program was not extensive enough to provide statistical probabilities for these events but did show that such events can occur. Damaging events required FORP or metal salts to be present at the initial mixing of MMH and NTO. Based on the results of these studies, it is suggested that removal or mitigation of a buildup of these materials may decrease the incidence of these high-energy, potentially damaging events.

Source record↗
NASA NTRS1982

Method of densifying an article formed of reaction bonded silicon nitride

A method of densifying an article formed of reaction bonded silicon nitride is disclosed. The reaction bonded silicon nitride article is packed in a packing mixture consisting of silicon nitride powder and a densification aid. The reaction bonded silicon nitride article and packing powder are sujected to a positive, low pressure nitrogen gas treatment while being heated to a treatment temperature and for a treatment time to cause any open porosity originally found in the reaction bonded silicon nitride article to be substantially closed. Thereafter, the reaction bonded silicon nitride article and packing powder are subjected to a positive high pressure nitrogen gas treatment while being heated to a treatment temperature and for a treatment time to cause a sintering of the reaction bonded silicon nitride article whereby the strength of the reaction bonded silicon nitride article is increased.

Mangels, John A.↗
NASA NTRS2019

Finding Evidence of a Prebiotic Pyruvate Reaction Network in Meteorites

The organic compounds of carbonaceous chondrites are structurally diverse products of the prolonged abiotic chemistry that occurred before and during the early stages of the solar system. They also represent the types of prebiotic compounds that may have participated in chemical evolutionary processes that gave rise to life. Pyruvic acid is a key component of primary metabolism that has recently been found in carbonaceous chondrites. Its prominence in biology has inspired us to explore its chemistry and possible role in the origin of metabolism. Our laboratory investigations have found that pyruvate (the ionized form of pyruvic acid) can serve as a single-source reactant to generate what we term a pyruvate reaction network (PRN). The core of the PRN is driven by pyruvate aldol polymerization and decay reactions. These decay reactions lead to the production of stable and unstable compounds which include mono, di, and tricarboxylic acids and a variety of keto acids. Importantly, many of these reactions apparently lead back to pyruvate, establishing a feedback process. Finding evidence of this reaction network in meteorites would establish that the chemistry of pyruvate did occur in a prebiotic environment and indeed many of the known compounds found in pyruvate reaction mixtures were detected in the Murchison and Murray meteorites. However, multiple synthetic origins, not tied to pyruvate chemistry, might also explain their meteoritic presence. Thus finding compounds unique to the PRN, such as reaction intermediates, would provide stronger evidence in support of its prebiotic relevance. The identity of these intermediates can only be con-firmed by acquiring chemical standards, however, as most are not available commercially, we engaged in extensive chemical synthesis. Obtaining these standards also provides the opportunity to study their subsequent chemistry and roles in the PRN.

Rios, A. C.↗
NASA NTRS2019

Finding Evidence of a Prebiotic Pyruvate Reaction Network in Meteorites

The organic compounds of carbonaceous chondrites are structurally diverse products of the prolonged abiotic chemistry that occurred before and during the early stages of the solar system. They also represent the types of prebiotic compounds that may have participated in chemical evolutionary processes that gave rise to life. Pyruvic acid is a key component of primary metabolism that has recently been found in carbonaceous chondrites. Its prominence in biology has inspired us to explore its chemistry and possible role in the origin of metabolism. Our laboratory investigations have found that pyruvate (the ionized form of pyruvic acid) can serve as a single-source reactant to generate what we term a pyruvate reaction network (PRN). The core of the PRN is driven by pyruvate aldol polymerization and decay reactions. These decay reactions lead to the production of stable and unstable compounds which include mono, di, and tricarboxylic acids and a variety of keto acids. Importantly, many of these reactions apparently lead back to pyruvate, establishing a feedback process. Finding evidence of this reaction network in meteorites would establish that the chemistry of pyruvate did occur in a prebiotic environment and indeed many of the known compounds found in pyruvate reaction mixtures were detected in the Murchison and Murray meteorites. However, multiple synthetic origins, not tied to pyruvate chemistry, might also explain their meteoritic presence. Thus finding compounds unique to the PRN, such as reaction intermediates, would provide stronger evidence in support of its prebiotic relevance. The identity of these intermediates can only be confirmed by acquiring chemical standards, however, as most are not available commercially, we engaged in extensive chemical synthesis. Obtaining these standards also provides the opportunity to study their subsequent chemistry and roles in the PRN.

Rios, Andro↗
NASA NTRS2020

Nuclear Fusion Reactions in Deuterated Metals

Nuclear fusion reactions of D-D are examined in an environment comprised of high density cold fuel embedded in metal lattices in which a small fuel portion is activated by hot neutrons. Such an environment provides for enhanced screening of the Coulomb barrier due to conduction and shell electrons of the metal lattice, or by plasma induced by ionizing radiation (γ quanta). We show that neutrons are far more efficient than energetic charged particles, such as light particles (e−, e+) or heavy particles (p, d, α) in transferring kinetic energy to fuel nuclei (D) to initiate fusion processes. It is well-known that screening increases the probability of tunneling through the Coulomb barrier. Electron screening also significantly increases the probability of large- versus small-angle Coulomb scattering of the reacting nuclei to enable subsequent nuclear reactions via tunneling. This probability is incorporated into the astrophysical factor S(E). Aspects of screening effects to enable calculation of nuclear reaction rates are also evaluated, including Coulomb scattering and localized heating of the cold fuel, primary D-D reactions, and subsequent reactions with both the fuel and the lattice nuclei. The effect of screening for enhancement of the total nuclear reaction rate is a function of multiple parameters including fuel temperature and the relative scattering probability between the fuel and lattice metal nuclei. Screening also significantly increases the probability of interaction between hot fuel and lattice nuclei increasing the likelilhood of Oppenheimer-Phillips processes opening a potential route to reaction multiplication. We demonstrate that the screened Coulomb potential of the target ion is determined by the nonlinear Vlasov potential and not by the Debye potential. In general, the effect of screening becomes important at low kinetic energy of the projectile. We examine the range of applicability of both the analytical and asymptotic expressions for the well-known electron screening lattice potential energy Ue, which is valid only for E >> Ue (E is the energy in the center of mass reference frame). We demonstrate that for E ≤ Ue, a direct calculation of Gamow factor for screened Coulomb potential is required to avoid unreasonably high values of the enhancement factor f (E) by the analytical—and more so by the asymptotic—formulas.

Vladimir Pines↗
NASA NTRS2022

The hierarchical organization of autocatalytic reaction networks and its relevance to origin of life

Abiogenesis has long been suspected to require that chemical reaction networks contain multiple autocatalytic cores, but little is known about what features of these networks allow for the gradual accretion of complexity. To identify realistic scenarios for the emergence of life-like properties, we develop the concept of a seed-dependent autocatalytic system (SDAS), which is a subnetwork that can autocatalytically self-maintain given a flux of food, but cannot be initiated by food alone. Rather, initiation of SDASs requires the transient introduction of chemical “seeds”. We show that, depending on the topological relationship of SDASs in a chemical reaction network, a food-driven system can accrete complexity in a historically contingent manner, governed by rare seeding events. We develop new algorithms for detecting and analyzing SDASs in chemical reaction databases and describe parallels between multi-SDAS networks and biological ecosystems. Applying our algorithms to both an abiotic reaction network and a biochemical one, each driven by a set of simple food chemicals, we detect SDASs that are organized as trophic tiers, of which the higher tier can be seeded by relatively simple chemicals if the lower tier is already activated. This indicates that sequential activation of trophically organized SDASs by seed chemicals that are not much more complex than what already exist could be a mechanism of gradual complexification from relatively simple abiotic reactions to more complex life-like systems. Interestingly, in both reaction networks, higher-tier SDASs include chemicals that might alter emergent features of chemical systems and could serve as early targets of selection. Our analysis provides computational tools for analyzing very large chemical/biochemical reaction networks and suggests new approaches to studying abiogenesis in the lab.

Zhen Peng↗
DOE OSTI2025

Unraveling Hydrogen Induced Geochemical Reaction Mechanisms through Coupled Geochemical Modeling and Machine Learning

Underground hydrogen storage (UHS) provides a promising large-scale, long-term energy storage solution. A reasonable recovery of stored hydrogen is critical for a successful storage scheme. However, in subsurface reservoirs hydrogen is subject to active geochemical reactions that might result in hydrogen loss. In this study, we implemented a geochemical modeling approach coupled with an unsupervised machine learning technique called non-negative matrix factorization (NMF) to unravel the complex brine-rock-H 2 geochemical processes responsible for hydrogen losses, with particular focus on sulfate reduction reactions. NMF is applied to modeled mineral evolution and fluid component profiles to retrieve profiles that can be interpreted to more easily assess competing processes. NMF decouples simulated competing equilibrium reactions. This facilitates separation of overlapping reaction profiles from redox processes, dissolution fronts, and secondary precipitation while considering the effects of simulation parameters such as salinity, temperature, and total H 2 pressure. NMF successfully discriminates these competing effects in nonlinear ways, allowing robust interpretation. In addition, NMF reveals subtle coupled mineral associations and reaction fronts that are invisible to conventional model analysis. This integrated approach strengthens the conceptual understanding of complex nonlinear hydrogen-brine-rock interactions and advances geochemical research on UHS systems to resolve complexities in modeled geochemical systems without the need for direct experiments or prior knowledge. Furthermore, this study highlights the efficacy of combining geochemical modeling with machine learning techniques to enhance the interpretability of the intricate geochemical simulation output through deciphering the overlapping reaction path that cannot be achieved only using conventional analysis of geochemical models alone.

08 HYDROGEN↗
DOE OSTI2024

Probing O 2 -dependence of cyclopentyl reactions via isomer-resolved speciation

Modeling chemical kinetics relevant to low-temperature combustion requires complete description of reactions involving critical species such as hydroperoxyalkyl radicals, Q̇OOH, which undergo competing unimolecular reactions and bimolecular reactions with O 2 . The balance of flux across the two pathways affects rates of chain-branching and depends on temperature, pressure, and oxygen concentration. Accordingly, the influence of [O 2 ] on product formation from alkyl + O 2 reactions and the subsequent fate of Q̇OOH and related products is central to the development of an accurate chemical kinetics mechanism. Furthermore, chemical reactions consuming Q̇OOH-mediated species are often simplified to such a degree that mechanism truncation error (uncertainty derived from incomplete reaction networks) becomes significant.

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

Nitromethane Decomposition via Automated Reaction Discovery and an Ab Initio Corrected Kinetic Model

In the explore the systematic construction of kinetic models from in silico reaction data for the decomposition of nitromethane. Our models are constructed in a computationally affordable manner by using reactions discovered through accelerated molecular dynamics simulations using the ReaxFF reactive force field. The reaction paths are then optimized to determine reaction rate parameters. We introduce a reaction barrier correction scheme that combines accurate thermochemical data from density functional theory with ReaxFF minimal energy paths. We validate our models across different thermodynamic regimes, showing predictions of gas phase CO and NO concentrations and high-pressure induction times that are similar to experimental data. The kinetic models are analyzed to find fundamental decomposition reactions in different thermodynamic regimes.

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

Fermi-Based Kinetic Model for the Sabatier Reaction: Sabatier Principle and Beyond It

The CO 2 methanation reaction (aka the Sabatier reaction) is one of the important carbon utilization technologies to reduce atmospheric greenhouse gases. In this study, kinetic modeling of the Sabatier reaction proceeding via the CO route has been presented by considering weak and strong chemisorption concepts rooted in electronic theory. Based on the single-route mechanism of the Sabatier reaction, the dependence of the reaction rate on the position of the catalyst Fermi level with respect to the antibonding states of the reagent (CO 2 ) and the product (CH 4 ), is demonstrated with the classic Sabatier volcano-shape. Furthermore, the model was applied to explain experimental results of reaction rates for Ni- and Ru-based catalytic systems and to understand origin of enhancement of turnover frequencies established for dynamic catalysis.

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

Signatures of Non-universal Quantum Dynamics of Ultracold Chemical Reactions of Polar Alkali Dimer Molecules with Alkali Metal Atoms: Li( 2 S) + NaLi( a 3 Σ + ) → Na( 2 S) + Li 2 ( a 3 Σ u + )

Ultracold chemical reactions of weakly bound triplet-state alkali metal dimer molecules have recently attracted much experimental interest. Here we perform rigorous quantum scattering calculations with a new ab initio potential energy surface to explore the chemical reaction of spin-polarized NaLi(a 3 Σ + ) and Li( 2 S) to form Li 2 (a 3 Σ u + ) and Na( 2 S). The reaction is exothermic and proceeds readily at ultralow temperatures. Significantly, we observe strong sensitivity of the total reaction rate to small variations of the three-body part of the Li 2 Na interaction at short range, which we attribute to a relatively small number of open Li 2 (a 3 Σ u + ) product channels populated in the reaction. This provides the first signature of highly non-universal dynamics seen in rigorous quantum reactive scattering calculations of an ultracold exothermic insertion reaction involving a polar alkali dimer molecule, opening up the possibility of probing microscopic interactions in atom+molecule collision complexes via ultracold reactive scattering experiments.

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

Mechanism of the Accelerated Water Formation Reaction under Interfacial Confinement

Subnanoscale spaces at the interface between weakly coupled thin films and their metal supports offer exciting opportunities for studying chemical reactions under confinement. Here, we investigated the kinetics of water formation (from hydrogen and chemisorbed oxygen) in the confined space at the interface between bilayer (BL) silica and a Ru(0001) support, compared to the reaction on the bare Ru(0001) surface. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments were carried out at different temperatures at elevated pressures of H 2 to follow the reaction kinetics. The apparent activation energy at the BL-silica/Ru(0001) interface was found to be 0.38 eV lower than that on bare Ru(0001), consistent with a recent report by Prieto et al. (Angew. Chem., Int. Ed.2018, 57(28), 8749–8753) carried out at lower H 2 pressures using low-energy electron microscopy. Density functional theory calculations revealed that the rate-limiting step in the direct hydrogenation pathway on the Ru(0001) surface is the first hydrogen addition step (*H + *O ↔ *OH). The confinement at the BL-silica/Ru(0001) interface only marginally affects the energy barrier of the first hydrogen addition. Instead, it activates an alternative disproportionation reaction pathway (*H 2 O + *O ↔ 2*OH). On the bare Ru(0001) surface, the disproportionation pathway can only occur at cryogenic temperatures or under high water vapor pressures. However, the presence of the BL-silica increases the desorption barrier for water molecules at the interface. The increased residence time allows trapped water molecules to react with chemisorbed oxygen to produce two *OH per H 2 O with an activation energy 0.25 eV lower than that of the first hydrogen addition step. Finally, this work reveals the origin of the observed accelerated water formation reaction at the BL-silica/Ru(0001) interface in the low-temperature regime (T < 350 K) and points to a route to engineer chemical reaction pathways by leveraging subnanoscale confined spaces at metal–oxide interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Low-energy cross-section measurement of the B 10 ( α , n ) N 13 reaction and its impact on neutron production in first-generation stars

Nucleosynthesis in the first generation of massive stars offers a unique setting to explore the creation of the first heavier nuclei in an environment free of impurities from earlier stellar generations. In later generations of massive stars, hydrogen burning occurs predominantly through the CNO cycles, but without the carbon, nitrogen, and oxygen to catalyze the reaction sequence, first stars would have to rely on the inefficient pp chains for their energy production. Observations of second and third generation stars show pronounced abundances of carbon and oxygen isotopes, which suggests a rapid conversion of the primordial abundances to heavier elements. While the triple-alpha-process primarily facilitates this conversion, there are alternative reaction sequences, such as 2 H(α,γ) 6 Li(α,γ) 10 B(α,n) 13 N, that may play a significant role. To study such alternate reaction pathways for production of carbon and heavier nuclei, a number of new measurements are needed. In this work, new measurements are reported for the 10 B(α,n) 13 N reaction, extending the cross section down to 575 keV incident α-particle energy. The measurements were made using a state-of-the-art deuterated liquid scintillator and a spectrum unfolding technique. An R-matrix analysis was performed in order to facilitate a comparison of the underlying nuclear structure with the reaction measurements. An unexpected upturn is observed in the low-energy S factor that indicates the presence of a new low-energy resonance. Finally, a revised reaction rate is determined that takes into account the present data as well as other previous measurements from the literature that were previously neglected.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Improved $^{95}\mathrm{Mo}$ neutron resonance parameters and astrophysical reaction rates

We report improved 95 Mo neutron resonance parameters and reaction rates are important for nuclear astrophysics, testing nuclear models, and nuclear criticality safety. However, despite many previous neutron-capture and total cross-section measurements on this nuclide, there still is much room for improvement as well as several discrepancies. For example, there are very few firm resonance spin and parity assignments; average resonance parameters are available only for each parity, the currently recommended astrophysical reaction rate results in disagreements between stellar models and meteoric isotopic anomalies, and there are substantial disagreements in the neutron-capture cross section at low energies important for nuclear criticality safety. To obtain an improved set of neutron resonance parameters and astrophysical reaction rates for 95 Mo. High-resolution neutron-capture and transmission data were measured at the Oak Ridge Electron Linear Accelerator (ORELA) using highly isotopically enriched 95 Mo samples. The neutron-capture apparatus, data reduction, and analysis were improved so that information contained in the γ-ray cascade following neutron capture were used to assign resonance J π values. Following this, simultaneous analysis of the new neutron-capture and transmission data was used to obtain resonance energies, gamma widths, and neutron widths and their uncertainties to a maximum energy of 10 keV. Accurate neutron-capture cross sections also were obtained for the unresolved resonance region to a maximum energy of 500 keV and, together with the new resonance parameters, used to calculate the astrophysical reaction rates in the temperature range from 5 to 30 keV. A vastly improved set of 95Mo neutron resonance parameters and an astrophysical reaction rate accurate to about 3% were obtained. Firm J π assignments were determined for 261 of the 314 observed resonances. This is a very large improvement over the previously published 32 firm J π assignments for 108 resonances. Also, the number of resonances having both firm J π assignments and Γ γ values was increased by almost a factor of 24—from 11 to 261. Neutron- and total-radiation-width distributions and average resonance spacings, average total radiation widths, and neutron strength functions were obtained for the six different s- and p-wave possibilities. Parameters for the lowest s-wave resonance, which is most important for criticality benchmarks, were obtained with high accuracy. Simple modification of the neutron-capture apparatus and expansion and improvement of data analysis techniques led to a large increase in firm J π assignments for 95 Mo neutron resonances. The resulting astrophysical reaction rate is 20%–30% larger than the currently recommended rate at s-process temperatures, which should lead to better agreement between stellar models and meteoric isotopic anomalies. The neutron-capture cross section at low energies is substantially larger than recommended in the latest evaluation, which is problematical for criticality benchmarks. The average resonance spacing as a function of spin and parity is significantly different from current models. The total-radiation-width distributions are significantly broader than predicted by theory and show significant departures from the expected Gaussian shapes.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗