Results for “nuclear structures and reactions” — Page 23

DOE OSTI2025

Microscopic optical potentials from a Green's function approach

Optical potentials are a standard tool in the study of nuclear reactions, as they describe the interaction between a target nucleus and a projectile. The use of phenomenological optical potentials built using experimental data on stable isotopes is widespread. Although successful in their dedicated domain, it is unclear whether these phenomenological potentials can provide reliable predictions for unstable isotopes. To address this problem, optical potentials based on microscopic nuclear structure input calculations prove to be crucial and are an important current line of research. In this work we present an explicit implementation of the Feshbach formalism for the systematic derivation of optical potentials using input from nuclear structure models. Numerical tools for the derivation of Green's functions associated with nonlocal potentials are presented. In conclusion, the new optical potential, based on the valence shell model, is applied to the calculations of 𝑛 + 24 Mg elastic scattering and yields a close agreement with the experimental data.

Direct reactions↗

NASA NTRS2011

Low Cost Nuclear Thermal Rocket Cermet Fuel Element Environment Testing

Deep space missions with large payloads require high specific impulse and relatively high thrust to achieve mission goals in reasonable time frames.1,2 Conventional storable propellants produce average specific impulse. Nuclear thermal rockets capable of producing high specific impulse are proposed. Nuclear thermal rockets employ heat produced by fission reaction to heat and therefore accelerate hydrogen, which is then forced through a rocket nozzle providing thrust. Fuel element temperatures are very high (up to 3000 K), and hydrogen is highly reactive with most materials at high temperatures. Data covering the effects of high-temperature hydrogen exposure on fuel elements are limited.3 The primary concern is the mechanical failure of fuel elements that employ high-melting-point metals, ceramics, or a combination (cermet) as a structural matrix into which the nuclear fuel is distributed. The purpose of the testing is to obtain data to assess the properties of the non-nuclear support materials, as-fabricated, and determine their ability to survive and maintain thermal performance in a prototypical NTR reactor environment of exposure to hydrogen at very high temperatures. The fission process of the planned fissile material and the resulting heating performance is well known and does not therefore require that active fissile material be integrated in this testing. A small-scale test bed designed to heat fuel element samples via non-contact radio frequency heating and expose samples to hydrogen is being developed to assist in optimal material and manufacturing process selection without employing fissile material. This paper details the test bed design and results of testing conducted to date.

Bradley, D. E.↗

DOE OSTI2023

Mechanochemical formation of highly stable amorphous calcium carbonate in calcium silicates: Potential long-term storage of CO 2 in cement

Here, we have investigated mechanochemical reactions with the calcium silicate wollastonite to probe potential mechanisms of sequestration and long-term storage of CO 2 as mineral carbonates in cement pastes. Wollastonite, CaSiO 3 , was milled under ambient and 13 C enriched CO 2 atmospheres. Milling induced a structure change from monoclinic wollastonite-2M to triclinic-1T, consistent with high pressure treatment. The results from solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy shows this process forms an extraordinarily stable amorphous calcium carbonate (ACC) phase that remains despite a high temperature dehydration treatment (130 °C) and persists in the same form after 3 yrs. of storage at ambient conditions. Thermogravimetric analysis (TGA) of these samples indicates that ACC is produced at the similar solid concentrations in both CO 2 -enriched and ambient atmospheres. The observation of meta-stable ACC due to wollastonite carbonation may play an important role in further exploration and optimization of mineral carbonation reactions for CO 2 capturing cement formulations.

13C solid-state NMR↗

DOE OSTI2021

Influence of nonstatistical properties in nuclear structure on emission of prompt fission neutrons

We report the Hauser-Feshbach fission-fragment decay (HF 3 D) model is extended to calculate the prompt fission neutron spectrum (PFNS) for the thermal-neutron-induced fission on 235 U, where the evaporated neutrons from all possible fission-fragment pairs are aggregated. By studying model parameter sensitivities on the calculated PFNS as well as nonstatistical behavior of low-lying discrete level spin distribution, we conclude that discrepancies between the aggregation calculation and the experimental PFNS seen at higher neutron emission energies can be attributed to both the primary fission-fragment yield distribution and the possible high spin states that are not predicted by the statistical theory of nuclear structure.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2026

Exploring Resonance Structures in the Partial-Wave Analysis of ¿p0 Photoproduction at GlueX

This thesis studies what happens when a photon (¿) collides with a proton (p) and produces a neutral omega (¿) and pion (p0) pair, with a recoiling proton (p'), expressed as ¿p ¿ ¿p0p'. We study this and other reactions to better understand the strong nuclear force; one of the four fundamental forces that govern all the physics of the universe. This force is specifically responsible for the binding and decay of subatomic particles, such as the ones here. While we understand the ¿ and p0, what we are actually interested in is a short-lived unknown particle X that decays via X ¿ ¿p0. There are a multitude of possible particles X can be, and so our focus in this work is to find out what X is by determining its properties from the particles we measure. We do this via an intricate analysis procedure known as “partial-wave analysis”. By analogy, one can think of our particle detector as a buoy, and the particles we want to analyze (X) as pebbles hitting a pond. The waves created by the pebble will move our buoy, giving us information about the pebble that produced the wave. However, when multiple pebbles hit our pond, the waves overlap and interfere with each other. Our buoy only can measure the complicated interfering result of all the waves. To disentangle this, our partial-wave analysis works by modeling this interference pattern so that we may infer the properties of the pebbles (particles) we produced. In this thesis, we review the relevant experimental history in photoproduction and related production mechanisms, as well as the theoretical foundations that motivate our measurement. We describe the methods used to collect our data at the GlueX experiment stationed at the Jefferson Lab accelerator facility in Newport News, Virginia. We then detail the selections we apply to ensure our events are almost exclusively ¿p ¿ ¿p0p'. We cover the intensity model, how we verify its capabilities, and finally present our results together with systematic studies. Our primary result is the detection of a b1(1235) meson interfering with a wide JPC = 1-- vector state, measured via a mass-independent partial-wave analysis. It provides precise experimental results that can be used as input for theoretical models of the reaction, yielding conclusions about the procedures responsible for how our universe behaves at its most basic level.

Scheuer, Kevin [College of William and Mary, Willi↗

NASA NTRS2011

Low Cost Nuclear Thermal Rocket Cermet Fuel Element Environment Testing

Deep space missions with large payloads require high specific impulse (Isp) and relatively high thrust in order to achieve mission goals in reasonable time frames. Conventional, storable propellants produce average Isp. Nuclear thermal rockets (NTR) capable of high Isp thrust have been proposed. NTR employs heat produced by fission reaction to heat and therefore accelerate hydrogen which is then forced through a rocket nozzle providing thrust. Fuel element temperatures are very high (up to 3000K) and hydrogen is highly reactive with most materials at high temperatures. Data covering the effects of high temperature hydrogen exposure on fuel elements is limited. The primary concern is the mechanical failure of fuel elements which employ high-melting-point metals, ceramics or a combination (cermet) as a structural matrix into which the nuclear fuel is distributed. It is not necessary to include fissile material in test samples intended to explore high temperature hydrogen exposure of the structural support matrices. A small-scale test bed designed to heat fuel element samples via non-contact RF heating and expose samples to hydrogen is being developed to assist in optimal material and manufacturing process selection without employing fissile material. This paper details the test bed design and results of testing conducted to date.

Bradley, David E.↗

DOE OSTI2025

Chemical Interaction of Palladium in Uranium Oxycarbide Nuclear Fuel Kernel

Chemical Interaction of Palladium in Uranium Oxycarbide Nuclear Fuel Kernel Jana Howard1,3, Guang Yang3, Haiyan Zhao1*, Patrick Warren4, Tiankai Yao3, Steven Cavazos4 Elizabeth Sooby Wood4*, Ching-heng Shiau2 1 University of Idaho, Environmental Science, Idaho Falls, Idaho, USA 2 Boise State University, Microscopy and Characterization Suite, Idaho Falls, Idaho, USA 3 Idaho National Laboratory, Idaho Falls, Idaho, USA 4 University of Texas San Antonio, Department of Physics and Astronomy, San Antonio, Texas, USA *Corresponding author: haiyanz@uidaho.edu; elizabeth.soobywood@utsa.edu Tri-structural Isotropic (TRISO) particle fuel is the preferred choice for the newest and next-generation high-temperature nuclear reactors due to its robust construction [1]. The fuel design effectively contains fission products inside the particle at extremely high temperatures [2]. However, the effect of transition metal fission products on fuel performance and structural integrity remains largely unknown, creating uncertainties in predicting fuel performance and potential failure mechanisms [2]. For example, palladium (Pd) has a strong tendency to form intermetallic phases with uranium (U). These new phases tend to be hard and brittle which could lead to fracture of fuel kernel during irradiation [3,4]. Pd is not normally produced in high concentrations in normal fission reactions however, driving the production of Pd into the locality of a Uranium Oxycarbide (UCO) nuclear fuel provides an opportunity to closely observe the diffusion and chemical interactions. This study focuses on detailed transmission electron microscopy characterization of the intermetallic phases formed by the interaction between a UCO kernel and a Pd bar after annealing at 1100 °C for 100 hours. Figure 1 provides an overview of the UCO kernel in contact with the Pd bar. The UCO-Pd sample surface was examined using a Focused Ion Beam (FIB) Quanta 3D FEG FEI in VCD detector mode at 10kV, 83pA to reveal surface features. Several key surface features in the interaction region were observed including: (1) a small area with dendritic microstructure, (2) color contrast near the UCO kernel and Pd boundary, and (3) darker and lighter regions throughout the sample surface. To analyze diffusion behavior, FIB was used to prepare lamellae from five different areas of the UCO-Pd sample, as well as one for the as-received sample. These lamellae were examined using a Scanning Transmission Electron Microscope ThermoFisher Spectra 300 (STEM-Spectra). Energy Dispersive Spectroscopy results confirmed the diffusion between the UCO fuel and Pd bar. Figure 2 shows the identified phases of UC, UO2, and Pd dispersed throughout the interaction region. It was also found that the Pd concentration decreases as the radial distance from the UCO-Pd interface increases. The Pd concentration was 36.93% atomic fraction 11µm from the interaction region then decreased to 7.51% atomic fraction at 257 µm away from the interaction region. Figure 3 shows how concentrations of U and Pd vary across the interaction zone, highlighting the extent of diffusion. This study confirms that Pd interacts with surrounding material to form U-Pd phase and diffusion zones. These diffusion zones vary in composition depending on its radial distance from the point of contact with the Pd bar. These findings contribute to a deeper understanding of the fission product behavior in high temperature nuclear fuels, aiding in the prediction and mitigation of potential fuel degradation mechanisms. A B C Fig. 1. SEM micrographs of UCO fuel kernel in contact with solid Pd bar and the lift out locations. Figure 1A shows UCO fuel kernel in contact with solid Pd bar. Figure 1B shows a higher magnification image of the UCO fuel-Pd interaction zone. Figure 1C shows lift out sites for the lamellae. A B C Fig 2. EDS maps reveal the distribution of U, O, and Pd in location 3. Figure 2A shows the distribution of uranium. Figure 2B shows the distribution of oxygen. Figure 2C shows the distribution of palladium. A B C Fig 3. Palladium and uranium concentration across interaction zone in location 2. Figure 3A shows EDS map of lift out number 2. Figure 3B shows a zoomed in EDS map taken from the interaction zone. Figure 3C shows a line graph of uranium and palladium concentrations across the interaction zone. References: 1. B.E. Wells, N.R. Phillips, K.J. Geelhood. Pacific West Laboratory. (2021). TRISO Fuel: Properties and Failure Modes. https://www.nrc.gov/docs/ML2117/ML21175A152.pdf (Accessed January 16, 2025). 2. American Nuclear Society. TRISO Fuel Development Progresses in INL, ORNL. https://www.gen-4.org/gif/upload/docs/application/pdf/2014-03/nov13nn_fuel_reprint.pdf (Accessed January 16, 2025) 3. Clark R.A., M.A. Con

36 - MATERIALS SCIENCE↗

DOE OSTI2025

Chemical Interaction of Palladium in Uranium Oxycarbide Nuclear Fuel Kernel

Chemical Interaction of Palladium in Uranium Oxycarbide Nuclear Fuel Kernel Jana Howard1,3, Guang Yang3, Haiyan Zhao1*, Patrick Warren4, Tiankai Yao3, Steven Cavazos4 Elizabeth Sooby Wood4*, Ching-heng Shiau2 1 University of Idaho, Environmental Science, Idaho Falls, Idaho, USA 2 Boise State University, Microscopy and Characterization Suite, Idaho Falls, Idaho, USA 3 Idaho National Laboratory, Idaho Falls, Idaho, USA 4 University of Texas San Antonio, Department of Physics and Astronomy, San Antonio, Texas, USA *Corresponding author: haiyanz@uidaho.edu; elizabeth.soobywood@utsa.edu Tri-structural Isotropic (TRISO) particle fuel is the preferred choice for the newest and next-generation high-temperature nuclear reactors due to its robust construction [1]. The fuel design effectively contains fission products inside the particle at extremely high temperatures [2]. However, the effect of transition metal fission products on fuel performance and structural integrity remains largely unknown, creating uncertainties in predicting fuel performance and potential failure mechanisms [2]. For example, palladium (Pd) has a strong tendency to form intermetallic phases with uranium (U). These new phases tend to be hard and brittle which could lead to fracture of fuel kernel during irradiation [3,4]. Pd is not normally produced in high concentrations in normal fission reactions however, driving the production of Pd into the locality of a Uranium Oxycarbide (UCO) nuclear fuel provides an opportunity to closely observe the diffusion and chemical interactions. This study focuses on detailed transmission electron microscopy characterization of the intermetallic phases formed by the interaction between a UCO kernel and a Pd bar after annealing at 1100 °C for 100 hours. Figure 1 provides an overview of the UCO kernel in contact with the Pd bar. The UCO-Pd sample surface was examined using a Focused Ion Beam (FIB) Quanta 3D FEG FEI in VCD detector mode at 10kV, 83pA to reveal surface features. Several key surface features in the interaction region were observed including: (1) a small area with dendritic microstructure, (2) color contrast near the UCO kernel and Pd boundary, and (3) darker and lighter regions throughout the sample surface. To analyze diffusion behavior, FIB was used to prepare lamellae from five different areas of the UCO-Pd sample, as well as one for the as-received sample. These lamellae were examined using a Scanning Transmission Electron Microscope ThermoFisher Spectra 300 (STEM-Spectra). Energy Dispersive Spectroscopy results confirmed the diffusion between the UCO fuel and Pd bar. Figure 2 shows the identified phases of UC, UO2, and Pd dispersed throughout the interaction region. It was also found that the Pd concentration decreases as the radial distance from the UCO-Pd interface increases. The Pd concentration was 36.93% atomic fraction 11µm from the interaction region then decreased to 7.51% atomic fraction at 257 µm away from the interaction region. Figure 3 shows how concentrations of U and Pd vary across the interaction zone, highlighting the extent of diffusion. This study confirms that Pd interacts with surrounding material to form U-Pd phase and diffusion zones. These diffusion zones vary in composition depending on its radial distance from the point of contact with the Pd bar. These findings contribute to a deeper understanding of the fission product behavior in high temperature nuclear fuels, aiding in the prediction and mitigation of potential fuel degradation mechanisms. A B C Fig. 1. SEM micrographs of UCO fuel kernel in contact with solid Pd bar and the lift out locations. Figure 1A shows UCO fuel kernel in contact with solid Pd bar. Figure 1B shows a higher magnification image of the UCO fuel-Pd interaction zone. Figure 1C shows lift out sites for the lamellae. A B C Fig 2. EDS maps reveal the distribution of U, O, and Pd in location 3. Figure 2A shows the distribution of uranium. Figure 2B shows the distribution of oxygen. Figure 2C shows the distribution of palladium. A B C Fig 3. Palladium and uranium concentration across interaction zone in location 2. Figure 3A shows EDS map of lift out number 2. Figure 3B shows a zoomed in EDS map taken from the interaction zone. Figure 3C shows a line graph of uranium and palladium concentrations across the interaction zone. References: 1. B.E. Wells, N.R. Phillips, K.J. Geelhood. Pacific West Laboratory. (2021). TRISO Fuel: Properties and Failure Modes. https://www.nrc.gov/docs/ML2117/ML21175A152.pdf (Accessed January 16, 2025). 2. American Nuclear Society. TRISO Fuel Development Progresses in INL, ORNL. https://www.gen-4.org/gif/upload/docs/application/pdf/2014-03/nov13nn_fuel_reprint.pdf (Accessed January 16, 2025) 3. Clark R.A., M.A. Con

36 - MATERIALS SCIENCE↗

NASA NTRS1992

The conductive propagation of nuclear flames. I - Degenerate C + O and O + Ne + Mg white dwarfs

The paper determines the physical properties - speed, width, and density structure - of conductive burning fronts in degenerate carbon-oxygen (C + O) and oxygen-neon-magnesium (O + Ne + Mg) compositions for a grid of initial densities and compositions. The dependence of the physical properties of the flame on the assumed values of nuclear reaction rates, the nuclear reaction network employed, the thermal conductivity, and the choice of coordinate system are investigated. The occurrence of accretion-induced collapse of a white dwarf is found to be critically dependent on the velocity of the nuclear conductive burning front and the growth rate of hydrodynamic instabilities. Treating the expanding area of the turbulent burning region as a fractal whose tile size is identical to the minimum unstable Rayleigh-Taylor wavelength, it is found, for all reasonable values of the fractal dimension, that for initial C + O or O + Ne + Mg densities above about 9 x 10 exp 9 g/cu cm the white dwarf should collapse to a neutron star.

Timmes, F. X.↗

DOE OSTI2023

Thermal Hydraulic Modeling of an Advanced Nuclear Reactor using open-source MOOSE tools

The aim of this study is to develop model of a small High Temperature Gas cooled Reactor (HTGR) including the balance of plant. This microreactor produces electricity using the thermal power of the nuclear reaction. This work utilizes the MOOSE Multiphysics simulation tools, which are mainly developed at Idaho National Laboratory (INL, Idaho, United States of America). Its thermal-hydraulics and Heat conduction Modules are used to study the fluids behavior in the primary loop and power conversion system and their interactions with the heating structures. More specifically, one verifies that the temperatures, pressures and mass flow rates of the fluids in both loops are consistent and that, at the same time, all the power transfers occur as expected. Moreover, the various mechanical components characteristics (turbine, compressor, pump) are adapted to the reactor operating conditions. This first analysis is conducted using simplified and one-dimensional model for the core. Ultimately, the obtained results are used to build a higher fidelity core model. This step aims to verify that the initial simplified simulation is consistent with the three-dimensional core modeling. In addition, the calculated material temperatures are checked. This study provides a fairly complete model of the thermal hydraulic phenomena for a particular design of High Temperature Gas cooled Reactor.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2023

Nuclear Structure and Decay Data for A=167 Isobars

Experimental nuclear spectroscopic data are compiled and evaluated for 17 known nuclides of mass 167 (Sm, Eu, Gd, Tb, Dy, Ho, Er Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt), 23 years after the previous full evaluation by 2000Ba65. Detailed information is presented for each reaction and decay experiment. Combining all the available data, recommended values are provided for energies, spins and parities, and half-lives of levels, with energies, branching ratios and multipolarities of γ radiations, and characteristics of β and α radiations in radioactive decays. Here, the α decays of A=171 nuclei to A=167 daughters are included in this work, while for α decays of A=167 nuclei to A=163 daughters, consult Nuclear Data Sheets (2010Re03) or the ENSDF database for A=163. 167 Er, 167 Tm, 167 Yb, 167 Lu and 167 Ta are among the most extensively studied nuclides via decay and high-spin gamma-ray spectroscopy measurements, followed by 167 Ho, 167 Hf, 167 W, and 167 Os. Information for excited states in 167 Dy, 167 Re, and 167 Ir are limited; no excited states have yet been identified in 167 Sm, 167 Eu, 167 Gd, 167 Tb and 167 Pt, with the ground-state half-life of 167 Sm remaining unknown. This work supersedes the earlier evaluation of A=167 nuclei by 2000Ba65.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS2012

Compact Fuel Element Environment Test

Deep space missions with large payloads require high specific impulse (I(sub sp)) and relatively high thrust to achieve mission goals in reasonable time frames. Conventional, storable propellants produce average I(sub sp). Nuclear thermal rockets (NTRs) capable of high I(sub sp) thrust have been proposed. NTR employs heat produced by fission reaction to heat and therefore accelerate hydrogen, which is then forced through a rocket nozzle providing thrust. Fuel element temperatures are very high (up to 3,000 K) and hydrogen is highly reactive with most materials at high temperatures. Data covering the effects of high-temperature hydrogen exposure on fuel elements are limited. The primary concern is the mechanical failure of fuel elements that employ high melting point metals, ceramics, or a combination (cermet) as a structural matrix into which the nuclear fuel is distributed. It is not necessary to include fissile material in test samples intended to explore high-temperature hydrogen exposure of the structural support matrices. A small-scale test bed designed to heat fuel element samples via noncontact radio frequency heating and expose samples to hydrogen for typical mission durations has been developed to assist in optimal material and manufacturing process selection without employing fissile material. This Technical Memorandum details the test bed design and results of testing conducted to date.

Bradley, D. E.↗

DOE OSTI2022

Time-of-flight experiments for nuclear structure and astrophysics

Neutron-rich isotopes are atomic nuclei with a large neutron excess compared to their stable counter parts. Their study provides essential information to understand the properties of the nuclear interaction, and to model nuclear processes in extreme astrophysical environments where neutron-rich isotopes drive the chains of nuclear reactions. Experimentally, these unstable isotopes are difficult to study because of their short half-lives and low production yields at particle accelerator laboratories. The TOF-Bρ technique is a mass measurement technique specialized for experiments with fast beams of short-lived radioactive isotopes. In this project we used the technique for two experiments performed at the National Superconducting Cyclotron Laboratory to measure new masses of isotopes in the region of 112 Mo and 46 S. The experiments at the NSCL were complemented by the development of new timing radiation detectors and experimental techniques to improve the performance and reach of mass measurements on neutron-rich isotopes.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRSDate not supplied

NTAC Augmented Nuclear and Advanced Propulsion

Currently, there are two types of nuclear propulsion: Nuclear Thermal Propulsion (NTP) and Nuclear Electric Propulsion (NEP). Common to both types, a nuclear reactor generates heat energy to raise the temperature of propellant, or the generated heat energy is converted into electric power. The electricity generated powers propulsion systems, such as a Hall thruster, magnetoplasma dynamic (MPD) thruster, or variable specific impulse magnetoplasma rocket (VASIMR). Customarily, only the thermal energy output from nuclear reaction is considered for NTP and NEP systems. However, the nuclear fission reaction can also generate ~7 MeV of prompt gamma rays. Therefore, most designers of NTP and NEP systems incorporate safety features to shield against this radiation. An optimized design approach would be to integrate a Nuclear Thermionic Avalanche Cell (NTAC) within the NTP or NEP structure for converting this radiation energy into additional electric power, while also shielding gamma rays. Consequently, this study addresses several combinations of NTP and NEP structures with NTAC devices in order to achieve that goal.

NTAC↗

DOE OSTI2024

Phase equilibria of advanced technology uranium silicide-based nuclear fuel

The phases in uranium-silicide binary system were evaluated in regards to their stabilities, phase boundaries, crystal structures, and phase transitions. The results from this study were used in combination with a well assessed literature to optimize the U-Si phase diagram using the CALPHAD method. A thermodynamic database was developed, which could be used to guide nuclear fuel fabrication, could be incorporated into other nuclear fuel thermodynamic databases, or could be used to generate data required by fuel performance codes to model fuel behavior in normal or off-normal reactor operations. The U 3 Si 2 and U 3 Si 5 phases were modeled using the Compound Energy Formalism model with 3 sublattices to account for the variation in composition. The crystal structure used for the USi phase was the tetragonal with an I4/mmm space. Above 450°C, the U 3 Si 5 phase was modeled. The composition of the USi 2 phase was adjusted to USi 1.84 . The calculated invariant reactions and the enthalpy of formation for the stoichiometric phases were in agreement with experimental data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Dynamics in Flexible Pillar[ n ]arenes Probed by Solid-State NMR

Pillar[n]arenes are supramolecular assemblies that can perform a range of technologically important molecular separations which are enabled by their molecular flexibility. Here, we probe dynamical behavior by performing a range of variable-temperature solid-state NMR experiments on microcrystalline perethylated pillar[n]arene (n = 5, 6) and the corresponding three pillar[6]arene xylene adducts in the 100–350 K range. This was achieved either by measuring site-selective motional averaged 13 C 1 H heteronuclear dipolar couplings and subsequently accessing order parameters or by determining 1 H and 13 C spin–lattice relaxation times and extracting correlation times based on dipolar and/or chemical shift anisotropy relaxation mechanisms. We demonstrate fast motional regimes at room temperature and highlight a significant difference in dynamics between the core of the pillar[n]arenes, the protruding flexible ethoxy groups, and the adsorbed xylene guest. Additionally, unexpected and sizable 13 C 1 H heteronuclear dipolar couplings for a quaternary carbon were observed for p-xylene adsorbed in pillar[6]arene only, indicating a strong host–guest interaction and establishing the p-xylene location inside the host, confirming structural refinements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

{sup 58}Ni({sup 3}He,t){sup 58}Cu*({gamma}) Measurements with GODDESS to Constrain the Astrophysical Rate of {sup 57}Ni(p,{gamma}){sup 58}Cu

The observation of γ rays from the decay of 44Ti in the remnants of core-collapse supernovae (CCSNe) provides crucial information regarding the nucleosynthesis occurring in these events, as 44Ti production is sensitive to CCSNe conditions. The final abundance of 44Ti is also sensitive to specific nuclear input parameters, one of which is the 57Ni(p,γ) 58Cu reaction rate. A precise rate for 57Ni(p,γ) 58Cu is thus critical if 44Ti production is to be an effective probe into CCSNe. To experimentally constrain the 57Ni(p,γ) 58Cu rate, the structure properties of 58Cu were measured via the 58Ni(3He,t)58Cu*(γ) reaction using GODDESS (GRETINA ORRUBA Dual Detectors for Experimental Structure Studies) at Argonne National Laboratory’s ATLAS facility. Details of the experiment, ongoing analysis, and plans are presented.

Carmichael, S. R.↗

DOE OSTI2021

Dynamic Interconversion of Metal Active Site Ensembles in Zeolite Catalysis

Catalysis science is founded on understanding the structure, number, and reactivity of active sites. Kinetic models that consider active sites to be static and noninteracting entities are routinely successful in describing the behavior of heterogeneous catalysts. Yet, active site ensembles often restructure in response to their external environment and even during steady-state catalytic turnover, sometimes requiring non-mean-field kinetic treatments to describe distance-dependent interactions among sites. Such behavior is being recognized more frequently in modern catalysis research, with the advent of experimental methods to quantify turnover rates with increasing precision, an expanding arsenal of operando characterization tools, and computational descriptions of atomic structure and motion at chemical potentials and timescales increasingly relevant to reaction conditions. This review focuses on dynamic changes to metal active site ensembles on zeolite supports, which are silica-based crystalline materials substituted with Al that generate binding sites for isolated and low-nuclearity metal site ensembles. Metal sites can become solvated and mobilized during reaction, facilitating interactions among sites that change their nuclearity and function. Such intersite communication can be regulated by the zeolite support, resulting in non-single-site and potentially non-mean-field kinetic behavior arising from mechanisms of catalytic action that combine elements of those canonically associated with homogeneous and heterogeneous catalysis. Here, we discuss recent literature examples that document dynamic active site behavior in metal-zeolites and outline methodologies to identify and interpret such behavior. We conclude with our outlook on future research directions to develop this evolving branch of catalysis science and harness it for practical applications.

operando characterization↗