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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Spin fluctuations, absence of magnetic order, and crystal electric field studies in the Yb 3+ -based triangular lattice antiferromagnet Rb 3 ⁢Yb⁢(VO 4 ) 2

Here, we report a comprehensive experimental investigation of the structural, thermodynamic, static, and dynamic properties of a triangular lattice antiferromagnet Rb 3 ⁢Yb(VO 4 ) 2 . Through the analysis of magnetic susceptibility, magnetization, and specific heat, complemented by crystal electric field (CEF) calculations, we confirm the Kramers' doublet with effective spin 𝐽 eff = 1/2 ground state. Magnetic susceptibility and isothermal magnetization analysis reveal a weak antiferromagnetic interaction among the 𝐽 eff = 1/2 spins, characterized by a small Curie-Weiss temperature (𝜃$^{\textrm{LT}}_{\textrm{CW}}$ ≃−0.26 K) or a reduced exchange coupling (𝐽/𝑘 B ≃ 0.18 K). The 51 V NMR spectra and spin-lattice relaxation rate (1/𝑇 1 ) show no evidence of magnetic long-range-order down to 1.6 K but reflect strong influence of CEF excitations in the intermediate temperatures. At low temperatures, 1/𝑇 1 ⁡(𝑇) shows pronounced frequency dependence and 1/𝑇 1 vs field at different temperatures follows the scaling behavior, highlighting the role of paramagnetic fluctuations. The CEF calculations using the point charge approximation divulge a large energy gap ( ∼18.61 meV) between the lowest and second lowest energy doublets, further establishing Kramers' doublet as the ground state. Our calculations also reproduce the experimental magnetization and specific heat data and indicate an in-plane magnetic anisotropy. These findings position Rb 3⁢ Yb(VO 4 ) 2 as an ideal candidate to explore intrinsic quantum fluctuations and possible quantum spin-liquid physics in a Yb 3+ -based triangular lattice antiferromagnet.

Sebastian, Sebin J. [Indian Institute of Science E↗
DOE OSTI2024

Formation of Stable Radicals by Mechanochemistry and Their Application for Magic Angle Spinning Dynamic Nuclear Polarization Solid-State NMR Spectroscopy

High-field magic angle spinning (MAS) dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (SSNMR) is becoming a common technique for improving the sensitivity in NMR by the hyperpolarization of nuclear spins. Recently, we have shown that gamma irradiation is capable of creating long-lived free radicals that are amenable to MAS DNP in quartz and a variety of organic solids. Here, we demonstrate that mechanochemical ball milling is able to generate millimolar concentrations of stable radical species in diverse materials, such as polystyrene, cellulose, borosilicate glass, and fused quartz. High-field electron paramagnetic resonance (EPR) was used to obtain further insight into the nature of the radicals formed in ball milled quartz and borosilicate glass. Finally, we further show that radicals generated in quartz by ball milling can be used for solid-effect DNP. We obtained 29 Si DNP enhancements of approximately 114 and 33 at 110 K and room temperature, respectively, from a sample of ball milled quartz.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes

Here the low-valent rhenium(I) salt Na[Re(η 5 -Cp)(BDI)] (BDI = N,N'-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) was shown to react with various halide and chalcogenolate reagents, leading to the isolation of a series of rhenium(III)-halide and -pseudohalide complexes: Re(X)(η 5 -Cp)(BDI) (1-X, X = F, Cl, Br, I; 2, X = OTf) and Re(ER)(η 5 -Cp)(BDI) (3-ER, ER = SBn, SeBn, TePh). The 1 H NMR spectra of these complexes displayed sharp resonances shifted several ppm from typical diamagnetic regions, as well as distinct chemical shift trends down both the halide (with the exception of F) and chalcogenolate series, with both Cp and BDI backbone peaks moving downfield with increasing atomic number. Subsequent magnetic susceptibility measurements of the rhenium(III) halides 1-Cl, 1-Br, and 1-I indicated that these complexes display temperature-independent paramagnetism (TIP), with χ TIP values of 7.41(44) × 10 -4 to 1.50(51) × 10 -3 cm 3 mol -1 . Multireference complete active space self-consistent field (CASSCF) computations incorporating spin-orbit state mixing revealed small energy separations (1.7-3.0 kcal/mol) between thermally isolated ground states and the first excited spin-orbit states for the rhenium halides, confirming that low-lying excited states are responsible for the observed TIP behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2022

LiMo 8 O 10 : Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra

Here, polycrystalline LiMo 8 O 10 was prepared in a sealed Mo crucible at 1380 °C for 48 h using the conventional high-temperature solid-state method. The polar tetragonal crystal structure (space group I4 1 md) is confirmed based on the Rietveld refinement of powder neutron diffraction and 7 Li/ 6 Li solid-state NMR. The crystal structure features infinite chains of Mo 4 O 5 (i.e., Mo 2 Mo 4/2 O 6/2 O 6/3 ) as a repeat unit containing edge-sharing Mo 6 octahedra with strong Mo–Mo metal bonding along the chain. X-ray absorption near-edge spectroscopy of the Mo-L 3 edge is consistent with the formal Mo valence/configuration. Magnetic measurements reveal that LiMo 8 O 10 is paramagnetic down to 1.8 K. Temperature-dependent resistivity [ρ(T)] measurement indicates a semiconducting behavior that can be fitted with Mott’s variable range hopping conduction mechanism in the temperature range of 215 and 45 K. The ρ(T) curve exhibits an exponential increase below 5 K with a large ratio of ρ 1.8 /ρ 300 = 435. LiMo 8 O 10 shows a negative field-dependent magnetoresistance between 2 and 25 K. Heat capacity measurement fitted with the modified Debye model yields the Debye temperature of 365 K.

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

Mechanistic Insights into Adsorptive and Catalytic Reactions from Controllable Distributions of Metal Cations (Pd, Pt, Ni, Cr, Cu) as [M‐OH] +1 /1Al or M +2 /2Al in Zeolites

Anchoring divalent metal ions in the same zeolite framework with similar Si/Al ratio selectively as zeolite-bound M +2 or [M +2 -OH] +1 cationic species enables critical comparison of the species’ intrinsic reactivity for industrially and fundamentally relevant reactions. H-BEA zeolites with similar Si/Al ratios but differing framework Al siting were used to anchored multiple divalent metal cations (Ni, Pd, Pt, Cr, Cu) in the zeolite micropores. State-of-the-art infrared (IR) spectroscopy, electron paramagnetic resonance (EPR) measurements, including two-dimensional pulsed HYSCORE EPR, extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT) calculations together provide unambiguous evidence for the selective formation of divalent metal cations as M +2 /2Al species (for H-BEA prepared in the conventional hydroxide media), and [M +2 OH] +1 /1Al species for H-BEA prepared in HF. Solid-state proton-decoupled triple-quantum magic-angle spinning (3Q MAS) NMR measurements confirmed contrasting Al distributions in the two H-BEA zeolites, which led to a contrasting divalent cation speciation. The reactivities of the two cationic species were explored for catalytic and adsorptive applications in both organometallic homogeneous and heterogeneous catalysis. This work demonstrates their divergent reactivity in ethylene dimerization, ethylene oxidation (Wacker process), selective catalytic reduction (SCR) of NO, NO adsorption, and methane oxidation. Both M +2 /2Al and [M +2 OH] +1 /1Al cations are both active for ethylene dimerization, but [M +2 OH] +1 /1Al species show higher reaction rates for each Pd, Ni, Pt. [M +2 OH] +1 /1Al is active for acetaldehyde formation in Wacker ethylene oxidation. A new active site for ethylene oligomerization is proposed that possesses a terminal OH group (Cr-OH) in Phillips catalysts evident by a nearly inactive isolated Cr +2 /2Al species that contrast an active Cr─OH motif.

Divalent metal cations in a zeolite↗
DOE OSTI2025

Comparison of Ce( iv )/Th( iv )-alkynyl complexes and observation of a trans -influence ligand series for Ce( iv )

Organometallic cerium(iv) complexes have been challenging to isolate and characterize due to the strongly oxidizing nature of the cerium(iv) cation. Herein, we report two cerium(iv) alkynyl complexes, [Ce(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-CeTMS) and [Ce(TriNOx)(C[triple bond, length as m-dash]C-Ph)] (1-CePh) (TriNOx3- = tris(2-tert-butylhydroxylaminato)benzylamine), that include terminal alkyne moieties. The isostructural thorium analogue [Th(TriNOx)(C[triple bond, length as m-dash]C-SiMe3)] (1-ThTMS) was also synthesized and compared with 1-CeTMS in bond distance, 13C-NMR spectra, vibrational spectra and electronic structure. The Ce-C bond distances were 2.501(3) Å for 1-CePh and 2.513(5) Å for 1-CeTMS on the shorter end of the few reported CeIV-C single bonds (2.478(3)-2.705(2) Å), possibly indicating significant Ce 5d- and 4f-orbital involvement. 13C-NMR spectroscopy was also consistent with Ce-C covalency, with significantly deshielded resonances ranging from 185-213 ppm. Such 13C-NMR shifts demonstrate a strong influence from spin-orbit coupling (SOC) effects, corroborated by computational studies. Raman analysis showed ν C[triple bond, length as m-dash]C stretching frequencies of 2000 cm-1 (1-CeTMS) and 2052 cm-1 (1-CePh), indicating the cerium(iv)-alkynyl interaction, compared to the parent HC[triple bond, length as m-dash]CPh (IR = 2105 cm-1 and Raman = 2104 cm-1). L3-edge X-ray absorption measurements revealed a predominant Ce(iv) electronic configuration, and magnetic measurements revealed temperature-independent paramagnetism. Electrochemical studies similarly revealed the electron donating ability of the alkynyl ligands, stronger than either fluoride or imido ligands for the Ce(iv)(TriNOx)-framework, with a cerium(iv/iii) reduction potential of E pc = -1.58 to -1.66 V vs. Fc/Fc+. Evidence for a trans-influence has been observed by evaluating a series including previously reported [CeIV(TriNOx)X]+/0 complexes with axial ligands X = THF, I-, Br-, Cl-, F-, -C[triple bond, length as m-dash]C-Ph, -C[triple bond, length as m-dash]C-SiMe3, -NH(3,5-(CF3)2-Ar), -OSiPh3, -N(M(L))(3,5-(CF3)2-Ar) [M(L) = Li(TMEDA), K(DME)2 or Cs(2,2,2-crypt)]. These data stand in contrast with previous reports of an inverse trans-influence at cerium(iv) and point to differences in involvement of cerium 4f- versus 5d-orbitals in the electronic structures of the complexes.

Yang, Qiaomu↗
DOE OSTI2021

Structural insights into Lewis acid- and F4TCNQ-doped conjugated polymers by solid-state magnetic resonance spectroscopy

Molecular doping strategies facilitate orders of magnitude enhancement in the charge carrier mobility of organic semiconductors (OSCs). Understanding the different doping mechanisms and molecular-level constraints on doping efficiency related to the material energy levels is crucial to develop versatile dopants for OSCs. Given the compositional and structural heterogeneities associated with OSC thin films, insight into dopant–polymer interactions by long-range techniques such as X-ray scattering and electron microscopy is exceedingly challenging to obtain. This study employs short-range probes, solid-state (ss)NMR and EPR spectroscopy, to resolve local structures and intermolecular interactions between dopants such as F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), Lewis acid BCF (tris[pentafluorophenyl] borane) and Lewis base conjugated polymer, PCPDTBT (P4) (poly[2,6-(4,4-bis(2-hexadecyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]). Analysis of 1 H and 13 C ssNMR spectra of P4, P4 : F4TCNQ and P4 : BCF blends indicates that the addition of dopants induces local structural changes in the P4 polymer, and causes paramagnetism-induced signal broadening and intensity losses. The hyperfine interactions in P4 : BCF and P4 : F4TCNQ are characterized by two-dimensional pulsed EPR spectroscopy. For P4 : F4TCNQ, 19 F ssNMR analysis indicates that the F4TCNQ molecules are distributed and aggregated into different local chemical environments. By comparison, BCF molecules are intermixed with the P4 polymer and interact with traces of water molecules to form BCF–water complexes that serve as Brønsted acid sites, as revealed by 11 B ssNMR spectroscopy. These results indicate that the P4–dopant blends exhibit complex morphology with different distributions of dopants, whereby the combined use of ssNMR and EPR provides essential insights into how higher doping efficiency is observed with BCF and a mediocre efficiency is associated with F4TCNQ molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Terahertz EPR spectroscopy using a 36-tesla high-homogeneity series-connected hybrid magnet

Electron Paramagnetic Resonance (EPR) is a powerful technique to study materials and biological samples on an atomic scale. High-field EPR in particular enables extracting very small g-anisotropies in organic radicals and half-filled 3d and 4f metal ions such as Mn II (3d 5 ) or Gd III (4f 7 ), and resolving EPR signals from unpaired spins with very close g-values, both of which provide high-resolution details of the local atomic environment. Before the recent commissioning of the high-homogeneity Series Connected Hybrid magnet (SCH, superconducting + resistive) at the National High Magnetic Field Laboratory (NHMFL), the highest-field, high-resolution EPR spectrometer available was limited to 25 T using a purely resistive “Keck” magnet at the NHMFL. Herein, we report the first EPR experiments performed using the SCH magnet capable of reaching the field of 36 T, corresponding to an EPR frequency of 1 THz for g = 2. The magnet’s intrinsic homogeneity (25 ppm, that is 0.9 mT at 36 T over 1 cm diameter, 1 cm length cylinder) was previously established by NMR. We characterized the magnet’s temporal stability (5 ppm, which is 0.2 mT at 36 T over one-minute, the typical acquisition time) using 2,2-diphenyl-1-picrylhydrazyl (DPPH). This high resolution enables resolving the weak g-anisotropy of 1,3-bis(diphenylene)-2-phenylallyl (BDPA), Δg = 2.5 × 10 –4 obtained from measurements at 932 GHz and 33 T. Subsequently, we recorded EPR spectra at multiple frequencies for two Gd III complexes with potential applications as spin labels. In conclusion, we demonstrated a significant reduction in line broadening in Gd[DTPA], attributed to second order zero field splitting, and a resolution enhancement of g-tensor anisotropy for Gd[sTPATCN]-SL.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Impact of disorder on dynamics and ordering in the honeycomb-lattice iridate Na 2 IrO 3

Kitaev's honeycomb spin-liquid model and its proposed realization in materials such as α-RuCl 3 , Li 2 IrO 3 , and Na 2 IrO 3 continue to present open questions about how the dynamics of a spin liquid are modified in the presence of non-Kitaev interactions as well as the presence of inhomogeneities. Here we use 23 Na nuclear magnetic resonance to probe both static and dynamical magnetic properties in single-crystal Na 2 IrO 3 . We find that the NMR shift follows the bulk susceptibility above 30 K but deviates from it below; moreover below T N the spectra show a broad distribution of internal magnetic fields. Both of these results provide evidence for inequivalent magnetic sites at low temperature, suggesting inhomogeneities are important for the magnetism. The spin-lattice relaxation rate is isotropic and diverges at T N , suggesting that the Kitaev cubic axes may control the critical quantum spin fluctuations. Finally, in the ordered state, we observe gapless excitations, which may arise from site substitution, emergent defects from milder disorder, or possibly be associated with nearby quantum paramagnetic states distinct from the Kitaev spin liquid.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Nanoscale heterogeneity induced by nonmagnetic Zn dopants in the quantum critical metal CeCoIn 5 : 115 In NQR/NMR and 59 Co NMR study

We report antiferromagnetism in a prototypical quantum critical metal CeCoIn 5 is known to be induced by slight substitutions of nonmagnetic Zn atoms for In. In nominally 7% Zn-substituted CeCoIn 5 , an antiferromagnetic (AFM) state coexists with heavy fermion superconductivity. Heterogeneity of the electronic states is investigated in Zn-doped CeCoIn 5 by means of nuclear quadrupole and magnetic resonances (NQR and NMR). Site-dependent NQR relaxation rates 1/T 1 indicate that the AFM state is locally nucleated around Zn substituents in the matrix of a heavy fermion state, and percolates through the bulk at the AFM transition temperature T N . At lower temperatures, an anisotropic superconducting (SC) gap below the SC transition temperature Tc, and the SC state permeates through the AFM regions via a SC proximity effect. Applying an external magnetic field induces a spin-flop transition near 5T, reducing the volume of the AFM regions. Consequently, a short-ranged inhomogeneous AFM state survives and coexists with a paramagnetic Fermi liquid state at high fields.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Thermal and concentration effects on 1 H NMR relaxation of Gd 3+ -aqua using MD simulations and measurements

We report gadolinium-based contrast agents are key in clinical MRI for enhancing the longitudinal NMR relativity (r 1 ) of hydrogen nuclei ( 1 H) in water and improving the contrast among different tissues. The importance of MRI in clinical practice cannot be gainsaid, yet the interpretation of MRI relies on models with severe assumptions, reflecting a poor understanding of the molecular-scale relaxation processes. In a step towards building a clearer understanding of the relaxation processes, here we investigate thermal and concentration effects on r 1 of the Gd 3+ -aqua complex using both semi-classical molecular dynamics (MD) simulations and measurements. We follow the MD simulation approach recently introduced by [Singer et al., Phys. Chem. Chem. Phys., 2021, 23, 20974], in which no NMR relaxation model or free-parameter is assumed to predict r 1 , thereby bringing new insights into the physics of r 1 on a molecular scale. We expand the autocorrelation function G(t) in terms of molecular modes and determine the thermal activation energies of the two largest modes, both of which are consistent with the range of literature values for rotational diffusion. We also determine the activation energies for translational diffusion and low-field electron-spin relaxation, both of which are consistent with the literature. Furthermore, we validate the MD simulations at human body temperature and concentrations of the paramagnetic ion used in clinical MRI, and we quantify the uncertainties in both simulations and measurements.

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

The Response of Polarized Protons in Solid Hydrogen-Deuteride(HD) to Electron Beams

Solid frozen-spin polarized targets of hydrogen-deuteride(HD) have been proven advantageous in photon beam experiments, where they exhibit immeasurably long spin-relaxation times(T1). The present research investigates their potential applicability to experiments with minimum-ionizing charged-particle beams. Studies have been conducted with sub-nanoAmp CW currents of 10 MeV electron beams at the newly commissioned Upgraded Injector Test Facility (UITF) at Jefferson Lab (JLab). Since the energy deposition is almost independent of electron beam energy, these UITF experiments provide insight on the expected performance at the GeV energies required in typical JLab experiments. A horizontal in-beam dilution refrigerator equipped with superconducting solenoids has been used to maintain solid HD samples at about 0.1K and 1 Tesla. NMR coils sur rounding the HD target have been used to monitor hydrogen polarization. Thermal equilibrium polarizations of targets not in the frozen-spin state (with intentionally short T1) have been used to deduce the in situ temperature of solid HD while under electron bombardment. The behavior of a 40% H-polarized frozen-spin target has been tracked while exposed to beams under various conditions. Polarization loss has been observed to be approximately proportional to dose, with the target polarization dropping to 1/e of its initial value after about 6 µC cm2 , about 4 ? 1013 beam particles/cm2 . A model for depolarization by beam-associated paramagnetic impurities largely accounts for the data, and suggests that improvements in heat removal could lead to significant increases in the in-beam T1

Wei, Kevin↗
DOE OSTI2022

Determine the coordination of Al and Si of Fe-rich fly ash: The challenge in NMR and how we probe its heterogeneity using X-ray spectromicroscopy

Scanning transmission X-ray microscopy (STXM) coupled with ptychographic imaging at Al and Si K-edge is a new probe to the microscale chemistry of heterogenous materials. Here, the combined techniques are applied to study local coordination environment of Fe-rich fly ash (FA). Ptychographic imaging at Al K- and Si K-edge highlights the fine Al- and Si-rich morphological features, respectively, at 6 nm pixel resolution. STXM visualizes the inter- and intra-particle variations in the silicate polymerization degree and two types of Al coordination environment in FA. The Si K-edge of SiO4 connected with four-fold coordinated Al is higher than SiO4 sharing oxygen with six-fold coordinated Al. The result is consistent with bulk nuclear magnetic resonance spectroscopy measurement of the Fe-rich sample which, however, is sensitive to paramagnetic Fe and time-consuming. Here, we demonstrate that the combined method has great potential in the studies of chemically heterogenous aluminosilicates.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Topochemical Deintercalation of Li from Layered LiNiB: toward 2D MBene

The pursuit of two-dimensional (2D) borides, MBenes, has proven to be challenging, not the least because of the lack of a suitable precursor prone to the deintercalation. Here, we studied room-temperature topochemical deintercalation of lithium from the layered polymorphs of the LiNiB compound with a considerable amount of Li stored in between [NiB] layers (33 at. % Li). Deintercalation of Li leads to novel metastable borides (Li~ 0.5 NiB) with unique crystal structures. Partial removal of Li is accomplished by exposing the parent phases to air, water, or dilute HCl under ambient conditions. Scanning transmission electron microscopy and solid-state 7 Li and 11 B NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of Li~ 0.5 NiB and the mechanism of Li-deintercalation. We have shown that the deintercalation of Li proceeds via a “zip-lock” mechanism, leading to the condensation of single [NiB] layers into double or triple layers bound via covalent bonds, resulting in structural fragments with Li[NiB] 2 and Li[NiB] 3 compositions. The crystal structure of Li~ 0.5 NiB is best described as an intergrowth of the ordered single [NiB], double [NiB] 2 , or triple [NiB] 3 layers alternating with single Li layers; this explains its structural complexity. Here, the formation of double or triple [NiB] layers induces a change in the magnetic behavior from temperatureindependent paramagnets in the parent LiNiB compounds to the spin-glassiness in the deintercalated Li~ 0.5 NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).

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

Measurements of Electron Beam-Induced Spin-Relaxation in Frozen-Spin Hydrogen-Deuteride (HD)

Targets of solid hydrogen-deuteride (HD) can be prepared in a frozen-spin state with spin relaxation times (T1) in excess of a year. The present work has studied their potential use in experiments with electron beams. Polarization relaxation rates have been measured during exposure to sub-nanoAmp currents of 9.7 MeV electron beams from the recently commissioned Upgraded Injector Test Facility (UITF) at Jefferson Lab (JLab). These UITF measurements can be used to anticipate the expected performance at the GeV energies typical of JLab experiments, since the energy deposition in a target is almost independent of beam energy. An in-beam dilution refrigerator equipped with superconducting solenoids has been used to maintain solid HD samples at ?0.1 K and ?1 tesla, and internal NMR coils have been used to monitor hydrogen polarization. Spin-relaxation in two frozen-spin targets, with initial H-polarizations of 40% and 34%, have been tracked while exposed to beams under varying conditions of current, dose, beam duty factor and temperature. At a fixed accumulated dose, the spin-relaxation rates drop with current, suggesting depolarization by the charge cloud of the beam. Imposing a duty factor on the otherwise continuous UITF beam, with forced millisecond scale gaps, has shown no obvious correlation to polarization loss rates. After an accumulated dose of ?2 ?C/cm2, beam-off spin-relaxation rates drop from their immeasurably long pre-irradiation values to the order of weeks (with beam-on T1 values typically an order of magnitude shorter), reflecting a buildup of paramagnetic charge centers within the HD lattice. The accumulated polarization loss was approximately proportional to dose in both targets, dropping to 1/e of their initial values after ?6 ?C/cm2. Thermal equilibrium polarizations of targets not in the frozen-spin state (with intentionally short T1) have been used to deduce the in situ temperature of solid HD while under electron bombardment. A model for depolarization by beam-associated paramagnetic impurities largely accounts for the data, and suggests that improvements in heat removal could lead to significant increases in the in-beam T1.

O'Connell, Thomas↗
DOE OSTI2021

Iridate Li8IrO 6 : An Antiferromagnetic Insulator

In this work, a polycrystalline iridate Li 8 IrO 6 material was prepared via heating Li 2 O and IrO 2 starting materials in a sealed quartz tube at 650 °C for 48 h. The structure was determined from Rietveld refinement of room-temperature powder neutron diffraction data. Li 8 IrO 6 adopts the nonpolar space group $R\bar{3}$ with Li atoms occupying the tetrahedral and octahedral sites, which is supported by the electron diffraction and solid-state 7Li NMR. This results in a crystal structure consisting of LiO 4 tetrahedral layers alternating with mixed IrO 6 and LiO 6 octahedral layers along the crystallographic c -axis. The +4 oxidation state of Ir 4+ was confirmed by near-edge X-ray absorption spectroscopy. An in situ synchrotron X-ray diffraction study of Li 8 IrO 6 indicates that the sample is stable up to 1000 °C and exhibits no structural transitions. Magnetic measurements suggest long-range antiferromagnetic ordering with a Néel temperature (TN) of 4 K, which is corroborated by heat capacity measurements. The localized effective moment $μ_{\text{eff}}$ (Ir) = 1.73 $μ_{\text{B}}$ and insulating character indicate that Li 8 IrO 6 is a correlated insulator. First-principles calculations support the nonpolar crystal structure and reveal the insulating behavior both in paramagnetic and antiferromagnetic states.

36 MATERIALS SCIENCE↗
NASA NTRS1989

The 3-(bromoacetamido)-propylamine hydrochloride: A novel sulfhydryl reagent and its future potential in the configurational study of S1-myosin

Configurational study of S1-Myosin is an important step towards understanding force generation in muscle contraction. Previously reported NMR studies were corroborated. A new compound was synthesized, 3-(Bromoacetamido)-propylamine hydrochloride. Its potential as a sulfhydryl reagent provides an indirect but elegant approach towards future structural elucidation of S1-Myosin. The preliminary investigation has shown that this compound, BAAP, reacted with S1 in the absence of MgADP. The modified enzyme had a 2-fold increase in CaATPase activity and no detectable K-EDTA ATPase activity. Reaction of BAAP with S1 in the presence of MgADP resulted in a modified enzyme which retained a Ca-ATPase activity that was about 60 percent of the unmodified S1 and had essentially zero K-EDTA ATPase activity. Sulfhydryl titration indicated that about 1.5 and 3.5 SH groups per S1 molecule were blocked by BAAP in the absence and presence of MgADP, respectively. When coupled to a carboxyl group of EDTA, the resulting reagent could become a useful SH reagent in which chelated paramagnetic or luminescent lanthanide ions can be exploited to probe S1 conformation.

Sharma, Prasanta↗
DOE OSTI2021

Efficiency analysis of helium-cooled MAS DNP: case studies of surface-modified nanoparticles and homogeneous small-molecule solutions

Despite the growing number of successful applications of dynamic nuclear polarization (DNP)-enhanced magic-angle spinning (MAS) NMR in structural biology and materials science, the nuclear polarizations achieved by current MAS DNP instrumentation are still considerably lower than the theoretical maximum. Here, the method could be significantly strengthened if experiments were performed at temperatures much lower than those currently widely used (~100 K). Recently, the prospects of helium (He)-cooled MAS DNP have been increased with the instrumental developments in MAS technology that uses cold helium gas for sample cooling. Despite the additional gains in sensitivity that have been observed with He-cooled MAS DNP, the performance of the technique has not been evaluated in the case of surfaces and interfaces that benefit the most from DNP. Herein, we studied the efficiency of DNP at temperatures between ~30 K and ~100 K for organically functionalized silica material and a homogeneous solution of small organic molecules at a magnetic field B 0 = 16.4 T. We recorded the changes in signal enhancement, paramagnet-induced quenching and depolarization effects, DNP build-up rate, and Boltzmann polarization. For these samples, the increases in MAS-induced depolarization and DNP build-up times at around 30 K were not as severe as anticipated. In the case of the surface species, we determined that MAS DNP at 30 K provided ~10 times higher sensitivity than MAS DNP at 90 K, which corresponds to the acceleration of experiments by multiplicative factors of up to 100.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗