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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Leveraging slow $\mathrm{DOTA}$ f-element complexation kinetics to enable separations by kinetic design

The design of metal-concerned solvent extraction systems frequently leverages thermodynamically derived differences in selectivity. An alternative approach, leveraging kinetic control, has been considered much less seriously. Our recent manuscript describing DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) complexation kinetics across the lanthanide series shows the observed rate constant steadily increases across the series, with some non-monotonic behavior observed at terbium and thulium. This contrasts the thermodynamic stability constant trend, where lanthanide-DOTA stability constants initially increase and then plateau as a function of ionic radii after samarium. To leverage the kinetic differences of DOTA with the lanthanides across the series, kinetically based separations must be utilized. Since DOTA has very slow complexation kinetics, a separations system must expedite DOTA-metal complexation to allow a separation approximating practical application. Here in this report, a DOTA-based solvent extraction system, where DOTA is the aqueous holdback reagent and bis-2,4,4-trimethylpentylphosphinic acid (Cyanex 272) is the organic phase extractant, is demonstrated and compares the separations chemistry of Nd, Eu and Am. The slowness of DOTA complexation was addressed by heating the system. Results showed, in general, separation between metals is better during early phase contact, and diminishes under longer contact times. Under all conditions, separations are better than would be predicted based on a thermodynamic basis. This report suggests that while slowly complexing ligands classically used for biological applications may not be appropriate for thermodynamically designed metal separations, their use for kinetically based systems may be appropriate and enable a new design basis for f-element separations.

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

Competing Magnetic Interactions and the Role of Unpaired 4 f Electrons in Oxygen-Deficient Perovskites Ba 3 R Fe 2 O 7.5 ( R = Y, Dy)

Oxygen-deficient perovskite compounds with the general formula Ba 3 RFe 2 O 7.5 present a good opportunity to study competing magnetic interactions between Fe 3+ 3d cations with and without the involvement of unpaired 4f electrons on R 3+ cations. From analysis of neutron powder diffraction data, complemented by ab initio density functional theory calculations, we determined the magnetic ground states when R 3+ = Y 3+ (non-magnetic) and Dy 3+ (4f 9 ). They both adopt complex long-range ordered antiferromagnetic structures below T N = 6.6 and 14.5 K, respectively, with the same magnetic space group C a 2/c (BNS #15.91). However, the dominant influence of f-electron magnetism is clear in temperature dependence and differences between the size of the ordered moments on the two crystallographically independent Fe sites, one of which is enhanced by R–O–Fe superexchange in the Dy compound, while the other is frustrated by it. We report the Dy compound also shows evidence for temperature- and field-dependent transitions with hysteresis, indicating a field-induced ferromagnetic component below TN.

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

Stabilization of [(N 5 ) 2 BX] 2– and [(N 5 ) 2 B 2 X 2 ] 2– (X = H, F, Cl, Br) by Conjugation and Hyperconjugation Effects

The isolation of nucleophilic boron bases has led to a paradigm shift in boron chemistry. Previous studies of the bis(carbene) borylene complexes revealed that these compounds possess strong donor abilities, and their reaction inertness is due to the large steric hindrance between boron reagents and reactant. In the present study, we have theoretically studied the [(N 5 ) 2 BX] 2– and [(N 5 ) 2 B 2 X 2 ] 2– compounds (X = H, F, Cl, Br). Their electronic structures and properties are discussed by using the NBO, LOL, and ELF methods. We found that both π-conjugation and hyperconjugation effects can effectively stabilize the substituted nucleophilic anionic boron compounds [(N 5 ) 2 BX] 2– and [(N 5 ) 2 B 2 X 2 ] 2– . Substituents, especially X = H, stabilize the boron center through highly delocalized π-bonding, involving the formally “empty” in-plane p orbitals of the boron atom. While the halogen substituents have high electron withdrawal ability, leading to systems being less stable, we suggest the borinium anions [(N 5 ) 2 BH] 2– and [(N 5 ) 2 B 2 H 2 ] 2– as possible synthetic targets of novel environmentally friendly catalysts.

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

Energetic and Electronic Properties of AcX and LaX (X = O and F)

The bonding and spectroscopic properties of LaX and AcX (X = O and F) diatomic molecules were studied by highlevel ab initio CCSD(T) and SO-CASPT2 electronic structure calculations. Bond dissociation energies (BDEs) were calculated at the Feller−Peterson−Dixon (FPD) level. Potential energy curves and spectroscopic constants for the lowest-lying spin−orbit Ω states were obtained at the SO-CASPT2/aQ-DK level. A dense manifold of excited states was described for the monofluorides with the ground states well separated from the excited states. The spectroscopic parameters were in good agreement with those reported experimentally for LaO and LaF. For the diatomic molecules containing actinides, no experimental data of these parameters was found, but the results were consistent with other high-level calculations. The BDEs calculated at the FPD level were 791.3 (LaO), 705.2 (AcO), 650.0 (LaF), and 678.6 (AcF) kJ/ mol. The NBO analysis showed that the monofluorides are essentially ionic, which explains why the BDE(AcF) is higher than BDE(LaF); for the monoxides, covalent contributions involving the d orbitals of the metal and the p orbitals of the oxygen are stronger for LaO than AcO, which explains the higher BDE for LaO. Finally, the bond orders are predicted to be 2 for LaF and AcF, 3 for AcO, and higher than 3 for LaO.

Basis sets↗
DOE OSTI2023

Synergistic Coupling Effect of Electronic Conductivity and Interphase Compatibility on High-Voltage Na 3 V 2 (PO 4 ) 2 F 3 Cathodes

Na 3 V 2 (PO 4 ) 2 F 3 (NVPF) has been considered an up-and-coming cathode material candidate for sodium (Na) ion batteries in light of its high specific capacity and working voltage. However, an erratic cathode/electrolyte interface layer is inevitably formed, accompanied by continuous electrolyte decomposition on the NVPF surface, when the voltage exceeds 4.2 V vs Na + /Na. Herein, the interphase features of NVPF are obviously enhanced owing to the ameliorated electronic conductivity obtained by combining it with carbon nanotubes (CNT). The NVPF with 3 wt % CNT (NVPF@3% CNT) reduces the Na + diffusion kinetic energy barrier and electron transport resistance. Furthermore, the conducting network formed by CNT with sturdy structure strength can promptly accommodate the volumetric changes during sequential Na + extraction/insertion and thus effectively improve the long-term cyclic performance of NVPF/hard carbon full cells. The initial discharge capacity approaches 105 mA h g –1 at 0.5C, and it retains 94% capacity retention after 200 cycles at the temperature of –10 °C. The cathode/electrolyte interphase characterization results further demonstrate that the interphase layer on the NVPF@3% CNT cathode is thinner and more compact compared with pristine samples. Here, this research provides a competitive strategy to facilitate the interfacial compatibility between the NVPF and electrolytes and accelerate the commercialization of high-performance Na-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Effect of resistivity on poloidal asymmetries in electron density in the edge and scrape off layer in 3D full-F gyro-fluid simulations with FELTOR

In this contribution, we analyze the poloidal asymmetries in electron density in the edge and scrape-off layer (SOL) in a COMPASS-sized, diverted tokamak with the 3D full-F, isothermal, electromagnetic, and gyro-fluid model FELTOR. The study is performed for different simulations that span over 2 orders of magnitude in resistivity. The poloidal asymmetries of density are evaluated in the edge and the SOL relative to the outer midplane (OMP), where the highest densities are usually found. In the closed magnetic surfaces, the relative poloidal asymmetry with respect to the OMP is not larger than 20% independently of the plasma resistivity. For the open field lines in the SOL, the relative density asymmetry can range from 55% for the highest resistivity to around 40% for the lowest. The lowest densities inside the separatrix are found between the inner midplane and the top of the magnetic configuration, away from the X-point. In the SOL it is usually close to the X-point in the high field side. The observations in the closed field lines are consistent with ballooning transport but in the SOL oppose experimental evidence for high-density plasmas. In conclusion, this indicates the necessity for more complex physics to reproduce the experimental observations in the SOL for higher density plasmas, such as neutral-plasma dynamics and realistic divertor conditions.

3D full-f gyrofluid↗
DOE OSTI2022

Physical properties of the layered $\mathcal{f}$-electron van der Waals magnet Ce 2 Te 5

Here. we report a detailed study of the magnetic, transport, and thermodynamic properties of Ce 2 Te 5 single crystals, a layered $\mathcal{f}$-electron van der Waals magnet. Four consecutive transitions at ~5.2, 2.1, 0.9, and 0.4 K were observed in the ac-plane electrical resistivity $\rho(T)$, which were further confirmed in specific heat $C_\text{p}(T)$ measurements. Analysis of the magnetic susceptibility $\chi(T)$, the magnetic-field variation of $\rho(T)$, and the increase of the first transition temperature ($T_c$ ~ 5.2 K) with applied magnetic field indicates ferromagnetic order, while the decrease of the other transitions with field suggests different states with dominant antiferromagnetic interactions below $T_2$ ~ 2.1 K, $T_3$ ~ 0.9 K, and $T_4$ = 0.4 K. Critical behavior analysis around Tc that gives critical exponents $\beta$ = 0.31(2), $\gamma$ = 0.99(2), $\delta$ = 4.46(1), and $T_c$ = 5.32(1) K indicates that Ce 2 Te 5 shows a three-dimensional magnetic critical behavior. Moreover, the Hall resistivity ρxy indicates that Ce2Te5 is a multiband system with a relatively high electron mobility ~2900 cm 2 V –1 s –1 near $T_c$, providing further opportunities for future device applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Arabidopsis SnRK1 negatively regulates phenylpropanoid metabolism via Kelch domain-containing F-box proteins

Phenylpropanoid metabolism represents a substantial metabolic sink for the photosynthetically fixed carbon. The evolutionarily conserved Sucrose Non-Fermenting Related Kinase 1 (SnRK1) is a major metabolic sensor that reprograms metabolism upon carbon deprivation. However, it is not clear if and how SnRK1-mediated sugar signaling pathway controls phenylpropanoid metabolism. Here, we show that Arabidopsis SnRK1 negatively regulates phenylpropanoid biosynthesis via a group of Kelch domain-containing F-Box (KFB) proteins that are responsible for the ubiquitination and degradation of phenylalanine ammonia lyase (PAL). Down-regulation of AtSnRK1 significantly promoted the accumulation of soluble phenolics and lignin polymers and drastically increased PAL cellular accumulation but only slightly altered its transcription level. Co-expression of SnRK1α with PAL in Nicotiana benthamiana leaves resulted in the severe attenuation of the latter's protein level, but protein interaction assays suggested PAL is not a direct substrate of SnRK1. Furthermore, up- or down-regulation of AtSnRK1 positively affected KFB PALs gene expression, and energy starvation upregulated KFB PAL expression, which partially depends on AtSnRK1. Collectively, our study reveals that SnRK1 negatively regulates phenylpropanoid biosynthesis, and KFB PALs act as regulatory components of the SnRK1 signaling network, transcriptionally regulated by SnRK1 and subsequently mediating proteasomal degradation of PAL in response to the cellular carbon availability.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Laboratory Measurements of n >= 3 K-shell Transition Energies of Sulfur Ions from F-like S viii to Li-like S xiv

Inner-shell transitions are ubiquitous in nonequilibrium collisionally ionized plasmas, such as supernova remnants, and in photoionized plasmas, such as outflows from active galactic nuclei and X-ray binaries. Inner-shell X-ray emission can help determine key parameters of these systems, such as ionization time, τ, and ionization parameter, ξ. Despite their importance, only theoretical inner-shell transition energies are available for many ions. To provide experimental benchmarks, we have measured the dominant n → 1 K-shell transitions of sulfur ions where n ≥ 3 from Li-like S xiv to F-like S viii using LLNL’s SuperEBIT electron beam ion trap and the NASA/GSFC EBIT Calorimeter Spectrometer (ECS). We identify over 30 spectral features and measure their energies with uncertainties in the ∼0.1–1 eV range. We compare these results to Flexible Atomic Code (FAC) and multireference Møller–Plesset (MR-MP) calculations and find differences between theory and experiment of ∼1 eV for FAC and <0.5 eV for most MR-MP calculations. We also compare these results to two widely used atomic databases, AtomDB and CHIANTI, and find discrepancies as high as 7 eV. Furthermore, many transitions are missing from these databases despite being prominent in our data.

Atomic data benchmarking↗
DOE OSTI2022

f‐ block MOFs: A Pathway to Heterometallic Transuranics

Abstract A novel series of heterometallic f ‐block‐frameworks including the first examples of transuranic heterometallic 238 U/ 239 Pu‐metal–organic frameworks (MOFs) and a novel monometallic 239 Pu‐analog are reported. In combination with theoretical calculations, we probed the kinetics and thermodynamics of heterometallic actinide(An)‐MOF formation and reported the first value of a U‐to‐Th transmetallation rate. We concluded that formation of uranyl species could be a driving force for solid‐state metathesis. Density of states near the Fermi edge, enthalpy of formation, band gap, proton affinity, and thermal/chemical stability were probed as a function of metal ratios. Furthermore, we achieved 97 % of the theoretical maximum capacity for An‐integration. These studies shed light on fundamental aspects of actinide chemistry and also foreshadow avenues for the development of emerging classes of An‐containing materials, including radioisotope thermoelectric generators or metalloradiopharmaceuticals.

Park, Kyoung Chul↗
DOE OSTI2022

f‐ block MOFs: A Pathway to Heterometallic Transuranics

Abstract A novel series of heterometallic f ‐block‐frameworks including the first examples of transuranic heterometallic 238 U/ 239 Pu‐metal–organic frameworks (MOFs) and a novel monometallic 239 Pu‐analog are reported. In combination with theoretical calculations, we probed the kinetics and thermodynamics of heterometallic actinide(An)‐MOF formation and reported the first value of a U‐to‐Th transmetallation rate. We concluded that formation of uranyl species could be a driving force for solid‐state metathesis. Density of states near the Fermi edge, enthalpy of formation, band gap, proton affinity, and thermal/chemical stability were probed as a function of metal ratios. Furthermore, we achieved 97 % of the theoretical maximum capacity for An‐integration. These studies shed light on fundamental aspects of actinide chemistry and also foreshadow avenues for the development of emerging classes of An‐containing materials, including radioisotope thermoelectric generators or metalloradiopharmaceuticals.

Park, Kyoung Chul↗
DOE OSTI2020

Progress with the 5D full-F continuum gyrokinetic code COGENT

COGENT is an Eulerian gyrokinetic code being developed for edge plasma modelling. The code is distinguished by the use of a high-order finite-volume (conservative) discretization combined with mapped multi-block grid technology. Our recent work is focused on the development of a 5D full-F COGENT version.Anumerical algorithm utilizing locally a field-aligned multi-block coordinate system is implemented to facilitate simulations of highly anisotropic microturbulence in the presence of a strong magnetic shear. In this approach, the toroidal direction is divided into blocks such that,within each block, the cells are field-aligned and a non-matching (non-conformal) grid interface is allowed at the block boundaries. In this paper we report on details of the numerical implementation and present preliminary results of verification studies performed for the case of the ion temperature gradient (ITG) instability in a sheared toroidal annulus geometry.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

A Right-handed neutrino portal to the hidden sector: active neutrinos and their twins in an F-theory model

We analyze the neutrino phenomenology in an SU(5) F-theory model with both a visible sector and a twin hidden sector. At low energies, the strong and weak scales of the two sectors may differ but the spectrum of states is described by the MSSM (MSSM') in the visible (twin) sectors. What is special about the model is that there are right-handed neutrinos which couple to both sectors via Yukawa couplings. As a result, assuming 3 right-handed neutrinos with a large mass much greater than the weak scale, at tree-level the seesaw mechanism results in 3 massive Majorana neutrinos and 3 massless ones. The massless neutrinos acquire mass via radiative corrections. In our analysis, the massless neutrinos are predominantly active neutrinos, while the massive neutrinos are predominantly sterile neutrinos. We fit the active neutrino masses and mixing angles and discuss the phenomenology of the lightest sterile neutrino. Finally we consider some possible scenarios for cosmology.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Improved Statistics for F-theory Standard Models

Much of the analysis of F-theory-based Standard Models boils down to computing cohomologies of line bundles on matter curves. By varying parameters one can degenerate such matter curves to singular ones, typically with many nodes, where the computation is combinatorial and straightforward. The question remains to relate the (a priori possibly smaller) value on the original curve to the singular one. In this work, we introduce some elementary techniques (pruning trees and removing interior edges) for simplifying the resulting nodal curves to a small collection of terminal ones that can be handled directly. When applied to the QSMs, these techniques yield optimal results in the sense that obtaining more precise answers would require currently unavailable information about the QSM geometries. This provides us with an opportunity to enhance the statistical bounds established in earlier research regarding the absence of vector-like exotics on the quark-doublet curve.

Bies, Martin↗
DOE OSTI2020

Comparison Between the f-Electron and Conduction-Electron Density of States in the Falicov-Kimball Model at Low Temperature

The spinless Falicov-Kimball model is one of the simplest models of many-body physics. While the conduction-electron density of states is temperature independent in the normal state, the f -electron density of states is strongly temperature dependent—it has an orthogonality catastrophe singularity in the metallic phase and is gapped in the insulating phase. The question we address here is whether the spectral gap is the same for both electron species as T → 0. Finally, we find strong evidence to indicate that the answer is affirmative.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

The complex momentum representation approach and its application to low-lying resonances in ${^{17}}$O and ${^{29,31}}$F

Approaches for predicting low-lying resonances, uniformly treating bound, and resonant levels have been a long-standing goal in nuclear theory. Accordingly, we explored the viability of the complex momentum representation (CMR) approach coupled with new potentials. We focus on predicting the energy of the low-lying 2p 3/2 resonance in 17 O, which is critical for s-process nucleosynthesis and missing in previous theoretical research. Here, using a Woods-Saxon potential based on the Koning-Delaroche optical model and constrained by the experimental one-neutron separation energy, we successfully predicted the resonant energy of this level for the first time. Our predictions of the bound levels and 1d 3/2 resonance agree well with the measurement results. Additionally, we utilize this approach to study the near-threshold resonances that play a role when forming a two-neutron halo in 29,31 F. We found that the CMR-based predictions of the bound-level energies and unbound 1f 7/2 level agree well with the results obtained using the scattering phase shift method. Subsequently, we successfully found a solution for the 2p 3/2 resonance with energy just above the threshold, which is decisive for halo formation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗