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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO 4 Co–Mobility in the Nuclear Fuel Cycle

Spent nuclear fuel contains heavy element fission products that must be separated for effective reprocessing for a safe and sustainable nuclear fuel cycle. 93 Zr and 99 Tc are high-yield fission products that co-transport in liquid-liquid extraction processes. Here we seek atomic-level information of this co-extraction process, as well as fundamental knowledge about Zr IV (and Hf IV ) aqueous speciation in the presence of topology-directing ligands such as pertechnetate (TcO 4 – ) and non-radioactive surrogate perrhenate (ReO 4 – ). In this context, we show that the flat tetrameric oxyhydroxyl-cluster [M IV 4 (OH) 8 (H 2 O) 16 ] 8+ (and related polymers) is dissociated by perrhenate/pertechnetate to yield isostructural dimers, M 2 (OH) 2 (XO 4 – ) 6 (H 2 O) 6 • 3H 2 O (M=Zr/Hf IV ; X=Re/Tc VII ), elucidated by single-crystal X-ray diffraction. We used these model compounds to understand the pervasive 93 Zr- 99 Tc coextraction with further speciation studies in water, nitric acid, and tetrabutylphosphate (TBP) -kerosene; where the latter two media are relevant to nuclear fuel reprocessing. SAXS (small angle X-ray scattering), compositional evaluation, and where experimentally feasible, ESI-MS (electrospray ionization mass spectrometry) showed that perrhenate/pertechnetate influence Zr/Hf IV -speciation in water. Here, in Zr-XO 4 solvent extraction studies to simulate fuel reprocessing, we provide evidence that TcO 4 – enhances extraction of Zr IV , and compositional analysis of the extracted metal-complexes (Zr-ReO 4 study) is consistent with the crystallized Zr IV 2 (OH) 2 (Re VII O 4 – ) 6 (H 2 O) 6 •dimer.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Hydration of divalent lanthanides, Sm 2+ and Eu 2+ : A molecular dynamics study with polarizable AMOEBA force field

The chemistry of divalent lanthanides, Ln 2+ , is a growing sub-field of heavy element chemistry owing to new synthetic approaches. However, some theoretical aspects of these unusual cations are currently underdeveloped, especially as they relate to their dynamic properties in solution. In this study, we address the hydration of two of the classical Ln 2+ cations, Sm 2+ and Eu 2+ , using atomic multipole optimized energetic for biomolecular applications (AMOEBA) force fields. These cations have not been parameterized to date with AMOEBA, and few studies are available because of their instability with respect to oxidation in aqueous media. Coordination numbers (CN's) of 8.2 and 8.1 respectively for Sm 2+ and Eu 2+ , and 8.8 for both Sm 3+ and Eu 3+ have been obtained and are in good agreement with the few available AIMD and X-ray absorption fine structures studies. The decreased CN of Ln 2+ compared with Ln 3+ arises from progressive water exchange events that indicates the gradual stabilization of 8-coordinate structures with respect to 9-coordinate geometries. Moreover, the effects of the chloride counter anions on the coordination of Ln 2+ cations have been studied at different chloride concentrations in this work. Lastly, water exchange times of Ln 2+ cations have been calculated to provide a comprehensive understanding of the behavior of Eu 2+ and Sm 2+ in aqueous chloride media.

AMOEBA force field parameterization↗
DOE OSTI2025

Nuclear β − -decay with statistical de-excitation

he accurate description of nuclear β − -decay has far-reaching consequences for applications spanning nuclear reactors to the creation of heavy elements in astrophysical environments. We present the nuclear particle spectra associated with the β -decay of neutron-rich nuclei calculated with the well benchmarked coupled Quasi-particle Random Phase Approximation and Hauser–Feshbach (QRPA+HF) model. This approach begins with the population of the daughter nucleus via semi-microscopic Gamow-Teller or First-Forbidden strength distributions (QRPA) and follows the statistical de-excitation (HF) until the initial available excitation energy is exhausted. At each stage of de-excitation the emission by neutrons and $γ$-rays is considered obeying quantum mechanical selection rules. For completeness we also provide parsed Auger and Internal Conversion (IC) electron spectra from Evaluated Nuclear Data Files (ENDF). Our results are tabulated and provided in parsable ASCII formatted tables that are suitable for inclusion in various applications.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Investigation of potential polyatomic interferences on uranium isotope ratio measurements for the LS-APGD-Orbitrap MS system

The determination of actinide (e.g., U and Pu) content and isotopics is of importance to the nuclear forensics and safeguards communities. However, in the analysis of environmental samples, such as those collected by the International Atomic Energy Agency, uranium measurements can be complicated by isobaric interferences from polyatomic variants of heavy elements (e.g., Pb). This leads to complex, time-consuming sample manipulations (i.e., separations) before determining isotope ratios. An alternative strategy to sample pretreatment is to use high-resolution mass spectrometric platforms during the analysis to fully resolve the uranium isotopes from potential polyatomic interferences, negating the need for prior chemical separation. The liquid sampling - atmospheric pressure glow discharge (LS-APGD) coupled with an Orbitrap mass spectrometer provides a high-resolution (>70,000 m/Δm at m/z 200) inorganic mass spectrometry platform. Further, as a demonstration of the power of this instrumental platform, and indeed, the high-resolution approach in general, uranium isotope ratios were determined in the presence of elemental impurities (e.g., Pb, Pt, Ta, W) commonly encountered with environmental sample swipe analysis, without any prior treatment. Even at elemental impurity concentrations of 1000–5000× relative to uranium, no interference was observed with the 235 U or 238 U signal. In addition, the 235 U/ 238 U isotope ratio for the samples with the concomitants present are within 2 standard deviations of the values obtained without their addition, indicating that these impurities do not impact the determined uranium isotope ratio. These findings represent a significant first step in leveraging the high resolution of the LS-APGD-Orbitrap-MS to overcome isobaric and molecular interferences instead of relying on chemical separations.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Total absorption spectroscopy measurement on neutron-rich 74,75 Cu isotopes

This paper reports on the first β-decay study of 74,75 Cu isotopes using the technique of total absorption spectroscopy (TAS). The experiment was performed at the National Superconducting Cyclotron Laboratory at Michigan State University using the Summing NaI(Tl) (SuN) detector. The Cu isotopes are good candidates to probe the single-particle structure in the region because they have one proton outside the Z = 28 shell. Comparing the β-decay intensity distributions in the daughter Zn isotopes to the theoretical predictions provides a stringent test of the calculations. The nuclei in this region are also identified as playing an important role in the astrophysical r-process. Furthermore, the measured β-decay intensity distributions provide essential nuclear physics inputs required to better understand heavy element nucleosynthesis.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Atomic masses with machine learning for the astrophysical r process

The astrophysical r process plays a vital role in the production of heavy elements. Modeling of the r process is sensitive to masses and further requires knowledge of masses beyond current experimental reach. Therefore, simulations of the r process offer a unique test bed for predicting mass extrapolations. We take a Machine-Learning (ML) approach to model the masses across the entire chart of nuclides. For the first time, we simulate r-process nucleosynthesis with a physics-based ML mass model. We compare simulated abundances to solar data in order to evaluate the model's performance far from stability. The resulting r-process abundances up to thorium and uranium qualitatively match those of the observed solar system abundance pattern, with the characteristic peaks well positioned. We propagate the mass uncertainties obtained from the ML model to r-process abundance yields to estimate an uncertainty band associated with our approach. The size of the uncertainty band is approximately one order of magnitude which aligns with the uncertainty reported using alternative techniques.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Do we owe our existence to gravitational waves?

Two heavy elements essential to human biology are thought to have been produced by the astrophysical r-process, which occurs in neutron-rich environments: iodine is a constituent of thyroid hormones that affect many physiological processes including growth and development, body temperature and heart rate, and bromine is essential for tissue development and architecture. Collisions of neutron stars (kilonovae) have been identified as sources of r-process elements including tellurium, which is adjacent to iodine in the periodic table, and lanthanides. Neutron-star collisions arise from energy loss due to gravitational-wave emission from binary systems, leading us to suggest that gravitational waves have played a key role in enabling human life by producing iodine and bromine. We propose probing this proposal by searching in lunar material for live 129 I deposited by a recent nearby kilonova explosion.

Human biochemistry↗
DOE OSTI2022

Theory of nuclear fission

Atomic nuclei are quantum many-body systems of protons and neutrons held together by strong nuclear forces. Under the proper conditions, nuclei can break into two (sometimes three) fragments which will subsequently decay by emitting particles. This phenomenon is called nuclear fission. Since different fission events may produce different fragmentations, the end-products of all fissions that occurred in a small chemical sample of matter comprise hundreds of different isotopes, including α particles, together with a large number of emitted neutrons, photons, electrons and antineutrinos. The extraordinary complexity of this process, which happens at length scales of the order of a femtometer, mostly takes less than a femtosecond but is not entirely over until all the lingering β decays have completed – which can take years – is a fascinating window into the physics of atomic nuclei. While fission may be more naturally known in the context of its technological applications, it also plays a crucial role in the synthesis of heavy elements in astrophysical environments. In both cases, simulations are needed for the many systems or energies inaccessible to experiments in the laboratory. In this context, the level of accuracy and precision required poses formidable challenges to nuclear theory. Overall, the goal of this article is to provide a comprehensive overview of the theoretical methods employed in the description of nuclear fission.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Strong Magnetocrystalline Anisotropy Arising from Metal–Ligand Covalency in a Metal–Organic Candidate for 2D Magnetic Order

Layered metal–organic frameworks are promising candidates for new two-dimensional magnets, as their synthetic programmability of these materials can provide a route to diverse structural and electronic properties. However, such framework materials typically lack the heavy elements that engender magnetocrystalline anisotropy in the monolayer ferromagnets reported to date. Alternative sources of magnetic anisotropy are therefore needed in these materials. Here, we report the synthesis of single crystals of the framework material (NMe 4 ) 2 [Fe 2 L 3 ] (H 2 L = 3,6-dichloro-2,5-dihydroxybenzoquinone) and evaluate the angular dependence of its magnetic properties. Oriented-crystal magnetization measurements reveal strong uniaxial anisotropy, where the easy axis is aligned with the crystallographic c axis. While the spin carriers of this structure are isotropic $S = ^5/_2$ Fe III metal centers and $S = ^1/_2$ organic linkers, the anisotropy energy of the framework material is comparable to that of reported 2D ferromagnets. Density functional theory calculations indicate that the observed magnetocrystalline anisotropy arises from ligand-to-metal charge transfer that enhances the magnetic anisotropy of the otherwise isotropic Fe centers, suggesting that metal–ligand covalency can be utilized as a general additive for the development of 2D magnets. These results in this study show the possibility for (NMe 4 ) 2 [Fe 2 L 3 ] to retain magnetic order down to the 2D monolayer limit. In addition, the combination of large magnetic anisotropy and semiconducting character in (NMe 4 ) 2 [Fe 2 L 3 ] highlights its potential as a new 2D magnetic semiconductor.

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

Synthesis and Transport Properties of the Family of Zintl Phases Ca 3 RESb 3 (RE = La–Nd, Sm, Gd–Tm, Lu): Exploring the Roles of Crystallographic Disorder and Core 4f Electrons for Enhancing Thermoelectric Performance

Zintl phases with complex crystal structures have been studied as promising candidate-materials for thermoelectric (TE) applications. Here, we report the syntheses of the family of rare-earth metal Zintl phases with the general formula Ca 4–x RE x Sb 3 (x ≈ 1; RE = La–Nd, Sm, Gd–Tm, Lu). The structural elucidation is based on refinements of single-crystal X-ray diffraction data for 12 unique chemical compositions. The cubic structure is confirmed as belonging to the anti-Th 3 P 4 structure type (space group I4¯3d, no. 220, Z = 4), where the Ca and RE atoms share the same atomic site with ca. 75% and 25% occupancies, respectively. Such crystallographic disordering of divalent Ca and trivalent RE atoms in the structure provides a pathway to intricate bonding. The latter, together with the presence of heavy elements such as Sb and the lanthanides, are expected to enhance the scattering probability of phonons, thereby leading to as low thermal conductivity κ as that of the ordered RE 4 Sb 3 . The drive of the hypothetical parent compound Ca 4 Sb 3 to be stabilized by alloying with rare-earth metals can be understood following the Zintl-Klemm concept, as the resultant formula may be rationalized as (Ca 2+ ) 3 RE 3+ (Sb 3– ) 3 , indicating the realization of closed-shell electronic configurations for all elements. This notion is confirmed by electronic structure calculations, which reveal narrow bandgaps E g = 0.77 and 0.53 eV for Ca 3 LaSb 3 and Ca 3 LuSb 3 , respectively. Additionally, the incorporation of RE atoms into the structure drives the phase into a state of a degenerate semiconductor with dominant hole charge carriers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

From Three-Dimensional Clathrates to Two-Dimensional Zintl Phases AMSb 2 (A = Rb, Cs; M = Ga, In) Composed of Pentagonal M–Sb Rings

Three new antimonide Zintl phases, RbGaSb 2 , CsGaSb 2 , and CsInSb 2 , were discovered during exploration of corresponding A–M–Sb (A = Rb, Cs; M = Ga, In) ternary systems while searching for new clathrates. The AGaSb 2 phases crystallize in the tetragonal space group P4 2 /nmc (No. 137) in the LiBS 2 structure type, while CsInSb 2 crystallizes in lower symmetry in the orthorhombic space group Cmce (No. 64) in the KGaSb 2 structure type with additional disorder of one of the Cs sites. The crystal structures of all three reported AMSb 2 compounds are composed of two-dimensional [MSb 2 ] – tetrahedral layers separated by Rb + or Cs + cations. [MSb 2 ] – layers are built from fused M–Sb pentagons and hexagons, which are also the main structural units for A 8 M 27 Sb 19 clathrate cages. The semiconductor nature of AMSb 2 was suggested by band structure calculations and confirmed by transport property characterization. CsGaSb 2 is a rare example of an n-type pnictide Zintl phase. Finally, all reported compounds exhibit low thermal conductivity typical for complex antimonides of heavy elements.

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

Post-Mortem Characterization of Cerium Speciation in Molten Calcium Chloride

Abstract Advancing radiochemistry and nuclear materials science requires understanding actinide interactions with molten salts, which are used in next-generation nuclear reactors and for processing of actinides to recover useful fissile material. Understanding chemical interactions of actinides with molten salts has been limited by challenges in developing spectroscopic and X-ray techniques that are compatible with the high temperatures necessary to study molten salts. In this work, interactions of CeO2 (serving as a nonradioactive surrogate for uranium and plutonium) with CaCl2 are characterized following heating. Scanning electron microscopy indicates CeO2 morphological changes from small (<1 μm) particles to 3–5 μm sheets. Powder X-ray diffraction and infrared and Raman spectroscopies show the formation of CeOCl at higher (850–1050 °C) temperatures. In the absence of a chemical reducing agent, it was found that a high-temperature, low-oxygen environment is the key to the formation of oxychloride and that oxychloride formation is inhibited by annealing the CeO2 starting material. Lastly, thermal analysis revealed lowering of the melting point of CaCl2 after heating with CeO2. In all, this work identifies applicable spectroscopic techniques to target studies of heavy elements in molten salt environments and highlights the relationship between chemical speciation and melting behavior, a key thermophysical property.

Kelly, Sheridon N. [Lawrence Livermore National La↗
DOE OSTI2024

Quantum Molecular Charge-Transfer Model for Multistep Auger–Meitner Decay Cascade Dynamics

The fragmentation of molecular cations following inner-shell decay processes in molecules containing heavy elements underpins the X-ray damage effects observed in X-ray scattering measurements of biological and chemical materials, as well as in medical applications involving Auger electron-emitting radionuclides. Traditionally, these processes are modeled using simulations that describe the electronic structure at an atomic level, thereby omitting molecular bonding effects. This work addresses the gap by introducing a novel approach that couples Auger–Meitner decay to nuclear dynamics across multiple decay steps, by developing a decay spawning dynamics algorithm and applying it to potential energy surfaces characterized with ab initio molecular dynamics simulations. We showcase the approach on a model decay cascade following K-shell ionization of IBr and subsequent Kβ fluorescence decay. We examine two competing channels that undergo two decay steps, resulting in ion pairs with a total 3+ charge state. This approach provides a continuous description of the electron transfer dynamics occurring during the multistep decay cascade and molecular fragmentation, revealing the combined inner-shell decay and charge transfer time scale to be approximately 75 fs. In conclusion, our computed kinetic energies of ion fragments show good agreement with experimental data.

Ab initio molecular dynamics↗
DOE OSTI2025

COLUMBUS─An Efficient and General Program Package for Ground and Excited State Computations Including Spin–Orbit Couplings and Dynamics

The COLUMBUS program system provides the tools for performing high-level multireference (MR) computations, including the multireference configuration interaction (MRCI) method and its multireference averaged quadratic coupled cluster (MR-AQCC) extension, allowing computations on a wide range of fascinating atomic and molecular systems, including the treatment of open-shells and complicated excited state phenomena. The inclusion of spin−orbit coupling (SOC) directly within the MRCI step enables the description of systems containing heavy elements, such as lanthanides and actinides, whose properties are strongly influenced by SOC. Analytic energy gradients and nonadiabatic couplings at the correlated MRCI level provide the foundation for a variety of dynamics studies, giving insight into ultrafast photochemistry. New and ongoing method developments in COLUMBUS include the computation of spin densities, improved descriptions of ionic states, enhancements to the AQCC method, and the porting of COLUMBUS to graphical processing units (GPUs). New external interfaces enable an enhanced description of electronic resonances and molecules in strong laser fields. This work highlights these new developments while providing a detailed account of the diverse applications of COLUMBUS in recent years.

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

Strong Relativistic Effects in Lanthanide-Based Single-Molecule Magnets

Lanthanide-based single-molecule magnets (SMMs) are promising building blocks for quantum memory and spintronic devices. Designing lanthanide-based SMMs with long spin relaxation time requires a detailed understanding of their electronic structure, including the crucial role of the spin-orbit coupling (SOC). While traditional calculations of SOC using the perturbation theory applied to a solution of the non-relativistic Schrödinger equation are valid for light atoms, this approach is questionable for systems containing heavy elements such as lanthanides. We investigate the accuracy of the perturbation estimates of SOC by variationally solving the Dirac equation for the [DyO] + molecule, a prototype of a lanthanide-based SMM. We show that the energy splittings between the M J states involved in spin relaxation depend on the interplay between strong SOC and dynamic electron correlations. Here, we demonstrate that this interplay affects the resonances between the spin and vibrational transitions, and, therefore, the spin relaxation time.

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

Atomic-Scale Imaging of Lithium Vacancies in a Battery Cathode by Multislice Electron Ptychography

Atomic-resolution imaging of battery materials is critical for identification of local defects and structural variations, which are tied to battery performance. However, since battery materials are, by design, optimized to allow ion motion in response to an applied electric field, they are also very sensitive to radiation damage by an electron beam. Image resolution is therefore severely constrained by the dose applied. Here, we show that multislice electron ptychography (MEP) can provide sub-ångström lateral resolution images of both light and heavy elements of a Li-ion battery cathode, along with nanometer-scale depth information and greater dose efficiency than conventional electron microscopy methods. Using the depth-sectioning capability of MEP, we have been able to obtain direct visualizations of Li vacancy clusters, atom column by atom column, in Li x Ni 0.33 Mn 0.33 Co 0.33 O 2 (NMC111) cathodes. This capability to track Li distributions will be valuable in understanding, informing, and optimizing electrode material design for ion storage and transfer.

batteries↗
DOE OSTI2025

Magnetic Properties Tuning via Broad Range Site Deficiency in Square Net Material UCu x Bi 2

HfCuSi 2 -type pnictogen compounds have recently been shown to be a versatile platform for designing materials with topologically nontrivial band structures. However, these phases require strict control over the electron count to tune the Fermi level, which can only be achieved in compositions with A 2+ M 2+ Pn 2 and A 3+ M + Pn 2 (A = lanthanides, M = transition metals, Pn = pnictogens P–Bi) charge distribution. While such lanthanide compounds have been thoroughly studied as candidate magnetic topological materials, their heavy element analogs with uranium and bismuth remain largely underexplored. In this report, we present the synthesis of UCu x Bi 2 single crystals and study their magnetic properties. Detailed structural analysis revealed that flux-grown crystals always form as a site-deficient UCu x Bi 2 composition, where x varies between 0.20 and 0.64. Magnetic property measurements revealed a dependence of the magnetic coupling on the Cu site deficiency, linearly changing the Néel temperature from 51 K for UCu 0.60 Bi 2 to 118 K for UCu 0.30 Bi 2 . Moreover, higher Cu concentration promotes a metamagnetic transition in highly magnetically anisotropic UCu 0.60 Bi 2 single crystals. We show that DFT calculations can successfully model site deficiency in the UCu x Sb 2 and UCu x Bi 2 systems. This work paves the way toward using the site deficiency to tune the Fermi level in more ubiquitous A 3+ M 2+ x Pn 2 phases, which previously have not been considered topological candidate materials due to unfavorable electron count.

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

Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes

Abstract Controlling the properties of heavy element complexes, such as those containing berkelium, is challenging because relativistic effects, spin-orbit and ligand-field splitting, and complex metal-ligand bonding, all dictate the final electronic states of the molecules. While the first two of these are currently beyond experimental control, covalent M‒L interactions could theoretically be boosted through the employment of chelators with large polarizabilities that substantially shift the electron density in the molecules. This theory is tested by ligating Bk III with 4’-(4-nitrophenyl)-2,2’:6’,2”-terpyridine (terpy*), a ligand with a large dipole. The resultant complex, Bk(terpy*)(NO 3 ) 3 (H 2 O)·THF, is benchmarked with its closest electrochemical analog, Ce(terpy*)(NO 3 ) 3 (H 2 O)·THF. Here, we show that enhanced Bk‒N interactions with terpy* are observed as predicted. Unexpectedly, induced polarization by terpy* also creates a plane in the molecules wherein the M‒L bonds trans to terpy* are shorter than anticipated. Moreover, these molecules are highly anisotropic and rhombic EPR spectra for the Ce III complex are reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗