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DOE OSTI2016

Near white light emitting ZnAl{sub 2}O{sub 4}:Dy{sup 3+} nanocrystals: Sol–gel synthesis and luminescence studies

Highlights: • ZnAl{sub 2}O{sub 4}:Dy{sup 3+} spinel synthesized using sol–gel method. • Characterized by XRD, SEM and PL spectroscopy. • Investigations of emission, excitation and lifetime properties. • Evaluation of defect centers and trap parameters of the system. • Evaluation of CIE indices of near white light emitting phosphor. - Abstract: ZnAl{sub 2}O{sub 4}:Dy{sup 3+} nanoparticles were synthesized using citrate sol–gel method and characterized systematically using X-ray diffraction, scanning electron microscopy and photoluminescence spectroscopy. Emission spectrum of pure ZnAl{sub 2}O{sub 4} shows intense violet blue emission under ultra violet irradiation. Based on electron paramagnetic resonance (EPR) results; it was attributed to presence of singly ionized oxygen vacancy centres in ZnAl{sub 2}O{sub 4}. On doping Dy{sup 3+} in ZnAl{sub 2}O{sub 4}, complete host–dopant energy transfer does not take place. Local structural investigation and lifetime measurements reveal that dysprosium ion is distributed between both Zn{sup 2+} and Al{sup 3+} sites. Near white light from ZnAl{sub 2}O{sub 4}:Dy{sup 3+} is attributed to combined host and dopant luminescence. The trap parameters such as activation energy (E) and frequency factor (s) for TSL glow peak 165 °C were determined using different heating rate method. Thermally stimulated emission showed the presence of oxygen related defect centre.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Low dimensional magnetism in MnNb{sub 2−x}V{sub x}O{sub 6}

Highlights: • Magnetic structure is reported from neutron diffraction. • We examine changes of Néel temperature versus V content. • Composition dependence of intra and inter chain exchange parameters are determined. • The temperature dependence of the Mn magnetic moment is determined for MnNb{sub 1.9}V{sub 0.1}O{sub 6}. - Abstract: The structural and magnetic properties of MnNb{sub 2−x}V{sub x}O{sub 6} samples were studied. These materials belong to the AB{sub 2}O{sub 6} class, which presents low-dimensional magnetism. Curie-Weiss fitting gives a negative Weiss temperature that is a characteristic of dominant antiferromagnetic interactions in paramagnetic region. Rietveld refinements of neutron diffraction data show that magnetic moments are aligned antiferromagnetically within the zig-zag chains running along the c axis. Unlike other ANb{sub 2}O{sub 6} type systems crystallizing also in Pbcn space group and presenting ferromagnetic Ising chains, MnNb{sub 2−x}V{sub x}O{sub 6} samples exhibit antiferromagnetic type order along the chains. At 1.5 K, the Mn atoms are found to carry an ordered magnetic moment of about 4.3 μ{sub B}. The Mn chains are antiferromagnetic and do not present significant anisotropy. These characteristics and the high spin allowed us to model the system as weakly interacting classical Heisenberg chains, estimating the values of both intra- and interchain exchange constants evolution with x content.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Preparation of Gd(OH){sub 3} large single crystals by solid KOH assisted hydrothermal method and their luminescent and magnetic properties

Highlights: • Gd(OH){sub 3} large single crystals were prepared by solid KOH assisted hydrothermal method. • The possible growth mechanism of Gd(OH){sub 3} large single crystals was proposed. • The Gd(OH){sub 3} samples emitted a strong narrow-band ultraviolet B (NB-UVB) light. • The Gd(OH){sub 3} samples showed good paramagnetic properties. - Abstract: Large single crystals of gadolinium hydroxide [Gd(OH){sub 3}] in the length of several millimeters were successfully prepared by using solid KOH assisted hydrothermal method. Gd(OH){sub 3} samples were characterized by X-ray diffraction (XRD), 4-circle single-crystal diffraction, Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). FESEM image shows hexagonal prism morphology for the Gd(OH){sub 3} large crystals. The possible growth mechanism of Gd(OH){sub 3} large single crystals was proposed. The photoluminescence and magnetic properties of Gd(OH){sub 3} species were investigated.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Effect of sintering temperature on structural, magnetic and electrical transport properties of La0.67Ca0.33MnO3 ceramics prepared by Plasma Activated Sintering

Highlights: • La{sub 0.67}Ca{sub 0.33}MnO{sub 3} were prepared by using Plasma Activated Sintering technology. • Detailed studies of sintering temperature effect on structural, magnetic and electrical transport behaviors were investigated. • The observed behaviors have been explained by oxygen vacancy effect in combination with grain size effect. - Abstract: La{sub 0.67}Ca{sub 0.33}MnO{sub 3} (LCMO) ceramics were prepared by Plasma Activated Sintering (PAS). The effect of sintering temperature on structural, magnetic and electrical transport properties of the LCMO ceramics were investigated. XRD and SEM characterizations of the LCMO ceramics indicated that all samples exhibited single orthorhombic phase. Also, through PAS dense LCMO ceramics were obtained. Certain interesting phenomena were observed from the PAS sintering temperature effect on the magnetic and transport behaviors of LCMO ceramics, which were significantly different from traditional sintering methods The magnetization decreased and the resistivity increased as the sintering temperature increased, whereas the T{sub C} and T{sub IM} shifted towards the lower temperature side. The conduction mechanism of all samples was electron-magnon scattering process in the ferromagnetic low-temperature region, while the paramagnetic high-temperature region mechanism was explained with the variable range hopping (VRH) model. All these behaviors were explained through the oxygen vacancy effect in combination with the grain size effect.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Scaling study of magnetic phase transition and critical behavior in Nd0.55Sr0.45Mn0.98Ga0.02O3 manganite

Highlights: • The sample of Nd{sub 0.55}Sr{sub 0.45}Mn{sub 0.98}Ga{sub 0.02}O{sub 3} was synthesized via a solid state reaction route. • The PM to FM phase transition of this sample is found to be of second-order. • The critical behaviors and scaling relation for Nd{sub 0.55}Sr{sub 0.45}Mn{sub 0.98}Ga{sub 0.02}O{sub 3} have also been investigated by modified Arrott plot and critical isotherm analysis. • The estimated critical exponents are close to the values for 3D-Ising model. - Abstract: Microscopic magnetic interactions and magnetism can be probed by studying the critical paramagnetic–ferromagnetic phase transition of magnetic materials. In this work, the critical behavior of the lightly Ga-doped manganites Nd{sub 0.55}Sr{sub 0.45}Mn{sub 0.98}Ga{sub 0.02}O{sub 3} (NSMGO) has been investigated. Scaling analysis reveals the critical exponents β = 0.308, γ = 1.197, and δ = 4.916, where their self-consistency and reliability are verified by the Widom scaling law and the scaling equation. These exponents indicate that the magnetic phase transition in NSMGO belongs to the anisotropic 3D-Ising universality class. Nevertheless, the asymptotic critical exponents β{sub eff} and γ{sub eff} are found to approach to the values of 3D-Heisenberg model, implying the existence of isotropic short-range magnetic interactions. We suggest that, although the Nd-based manganites possess a strong magnetocrystalline anisotropy, this effect can be partly averaged out in view of the present polycrystalline NSMGO. Therefore, in the asymptotic critical region, the phase transition reveals the crossover from the scaling of 3D-Ising toward 3D-Heisenberg universality class.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Study of the structural and magnetic phase-transitions and multiferroic properties in BiFeO3-Ba0.95Ca0.05TiO3 solid solutions

Highlights: • The detailed structural analysis has been done for (1-x) BiFeO{sub 3}-xBa{sub 0.95}Ca{sub 0.05}TiO{sub 3} (0.1 ≤ x ≤ 0.9). • The detailed magnetic behavior has been studied for (1-x) BiFeO{sub 3}-xBa{sub 0.95}Ca{sub 0.05}TiO{sub 3} (0.1 ≤ x ≤ 0.9). • The dielectric constant (ε') and the dielectric loss (ε'') versus frequency curves have been fitted by using Cole-Cole dispersion formula and non-Debye relaxation behavior has been found. • The weak magnetodielectric response (MD) has been found. • The non saturating P-E loops have been found for 0.7 ≤ x ≤ 0.9 samples. - Abstract: We synthesized (1-x) BiFeO{sub 3}-x Ba{sub 0.95}Ca{sub 0.05}TiO{sub 3} solid solutions for 0.1 ≤ x ≤ 0.9, using a solid-state-reaction. The XRD analysis reveals that a composition-driven rhombohedral-to-cubic and a cubic-to-tetragonal phase-transition occur at x ≈ 0.4 and x ≈ 0.7, respectively. The experiments show that BaCaTiO{sub 3}-substitution suppresses the spiral spin-structure, which leads to net magnetization. The samples have been found to exhibit magnetic order for 0.1 ≤ x ≤ 0.7 and paramagnetic behavior for x ≥ 0.8. The electrical conductivity increases with increasing frequency of the applied electric field. The dielectric measurements suggest a non-Debye type relaxation. The samples show magneto-dielectric response (MD) upto x = 0.5, with the highest MD of 11.61% at 10 kHz for x = 0.3. The maximum attainable remanent polarization (P{sub r}) ∼ 5.24 μC/cm{sup 2} was observed for x = 0.7.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Synthesis and magnetic properties of nanocrystalline Gd3Fe5O12 and GdFeO3 powders prepared by sol–gel auto-combustion method

Highlights: • Glycine-based gel was successfully applied in the preparation of Gd ferrites. • High-purity nanocrystalline Gd{sub 3}Fe{sub 5}O{sub 12} and GdFeO{sub 3} powders were synthesized. • Magnetic properties of nanocrystalline GdFeO{sub 3} and Gd{sub 3}Fe{sub 5}O{sub 12} were investigated. • Transition mechanism of magnetic phase was discussed in detail. - Abstract: Nanocrystalline GdFeO{sub 3} and Gd{sub 3}Fe{sub 5}O{sub 12} powders were prepared successfully by sol–gel auto-combustion method using a glycine-based gel. The as-prepared GdFeO{sub 3} and Gd{sub 3}Fe{sub 5}O{sub 12} powders presented spherical shape, and composed of continuous porous network structure due to the releasing of a large amount of gases during auto-combustion process. This special microstructure was significant for reducing the magnetic interactions between nanocrystalline powders. The Gd{sub 3}Fe{sub 5}O{sub 12} samples presented ferrimagnetic feature at low temperatures. At 10 K, the saturate magnetization is about 87.9 emu/g. As temperature increased to 300 K, the magnetization decreased rapidly since the thermal fluctuations changed the main magnetic spin ordering. The GdFeO{sub 3} samples presented antiferromagnetic feature at 5 K, and the magnetization reaches 109 emu/g at 50,000 Oe field. As temperature increased to 300 K, the antiferromagnetism decreased rapidly, and the magnetization curve presents linear tendency due to the dominant paramagnetism contribution of Gd{sup 3+} ions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2024

Type-II superconductivity at 9K in Pb–Bi alloy

In the present work, we report the synthesis of Pb–Bi alloy with enhanced Tc of up to 9K, which is higher than that of Pb. The alloy is synthesized via a solid-state reaction route in the vacuum-encapsulated quartz tube at 700°C in an automated furnace. The synthesized sample is characterized by X-ray Diffraction(XRD) and Energy dispersive X-ray analysis(EDAX) for its phase purity and elemental composition. Rietveld refinement of XRD reveals that the end product is a majority hexagonal Pb 7 Bi 3 , with minor rhombohedral Bi. The electronic transport measurement shows metallic behavior with the Debye temperature of 108K and a superconductivity transition temperature (T c ) below 9K, which is the maximum to date for any reported Pb–Bi alloy, Pb or Bi at ambient pressure. Partial substitution of Bi at the Pb site may modify the free density of electronic states within the BCS model to attain the optimum T c , which is higher by around 2K from the reported T c of Pb. The superconductor phase diagram derived from magneto-transport measurements reveals that the synthesized alloy is a conventional superconductor with an upper critical field (H c2 ) of 3.9 T, which lies well within the Pauli paramagnetic limit. The magnetization measurements carried out following ZFC(Zero Field Cool) protocols infer that the synthesized alloy is a bulk superconductor below 9K. The isothermal M-H(Magnetization vs. Field) measurements performed below T c establish it as a type-II superconductor. Furthermore, the specific heat capacity measurements show that the Pb–Bi alloy is a strongly coupled bulk superconductor below around 9K with possibly two superconducting gaps.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2017

The Electron Bifurcating FixABCX Protein Complex from Azotobacter vinelandii : Generation of Low-Potential Reducing Equivalents for Nitrogenase Catalysis

The biological reduction of dinitrogen (N 2 ) to ammonia (NH 3 ) by nitrogenase is an energetically demanding reaction that requires low-potential electrons and ATP; however, pathways used to deliver the electrons from central metabolism to the reductants of nitrogenase, ferredoxin or flavodoxin, remain unknown for many diazotrophic microbes. The FixABCX protein complex has been proposed to reduce flavodoxin or ferredoxin using NADH as the electron donor in a process known as electron bifurcation. Herein, the FixABCX complex from Azotobacter vinelandii was purified and demonstrated to catalyze an electron bifurcation reaction: oxidation of NADH (E m = -320 mV) coupled to reduction of flavodoxin semiquinone (E m = -460 mV) and reduction of coenzyme Q (E m = 10 mV). Knocking out fix genes rendered ..delta..rnf A. vinelandii cells unable to fix dinitrogen, confirming that the FixABCX system provides another route for delivery of electrons to nitrogenase. Characterization of the purified FixABCX complex revealed the presence of flavin and iron-sulfur cofactors confirmed by native mass spectrometry, electron paramagnetic resonance spectroscopy, and transient absorption spectroscopy. Transient absorption spectroscopy further established the presence of a short-lived flavin semiquinone radical, suggesting that a thermodynamically unstable flavin semiquinone may participate as an intermediate in the transfer of an electron to flavodoxin. A structural model of FixABCX, generated using chemical cross-linking in conjunction with homology modeling, revealed plausible electron transfer pathways to both high- and low-potential acceptors. Altogether, this study informs a mechanism for electron bifurcation, offering insight into a unique method for delivery of low-potential electrons required for energy-intensive biochemical conversions.

09 BIOMASS FUELS↗

DOE OSTI2025

Universal Nuclear Accident Dosimeter

The Lawrence Livermore National Laboratory (LLNL) Universal Nuclear Accident Dosimetry (UNAD) project is a four-year initiative aimed at advancing nuclear accident dosimetry methods. This article presents an overview of the research, key findings, and the progress made throughout the project. The primary goals included a background into the history of nuclear accident dosimetry, consolidating current dosimetry techniques within the NNSA/DOE complex, fostering collaboration among subject matter experts, and exploring novel technologies for potential implementation. The technical focus centered on investigating new and novel technologies, instrumentation methods, and analysis methods to develop recommendations for a potential nuclear accident dosimeter (NAD) to be universally deployed through the DOE complex. A multilaboratory and multinational Usergroup was established, conducting periodic meetings to facilitate knowledge exchange. The UNAD team has participated in two international nuclear accident dosimetry intercomparison exercises and one characterization exercise, where the existing LLNL NAD and a prototype alanine electron paramagnetic dosimeter NAD were deployed. Ongoing improvements are being made to the prototype NAD based on results from the exercises, laboratory studies, and collaboration with other laboratories. A machine learning algorithm to optimize the geometry and conversion factors of the current LLNL NAD is being implemented, and the resulting design will be tested in the next exercise. In conclusion, key lessons learned and future directions for the project are discussed.

Electron paramagnetic resonance spectroscopy↗

DOE OSTI2024

Venturing into Unexplored Phase Space: Synthesis, Structure, and Properties of MgCo 3 B 2 Featuring a Rumpled Kagomé Network

MgCo 3 B 2 , a novel ternary boride in a previously unexplored phase space, was synthesized using the hydride route. In situ powder X-ray diffraction and DFT calculations aided in the discovery of this compound, whose structure was then determined by single-crystal X-ray diffraction. Like the closely related CeCo 3 B 2 , MgCo 3 B 2 crystallizes in centrosymmetric space group P6/mmm (a = 4.883(2) Å, c = 2.926(2) Å at 210 K, Z = 1). Unlike CeCo 3 B 2 , however, it adopts a disordered structure that features a rumpled Kagomé network of Co atoms, and Mg atoms fill the channels of a Co–B framework. Although the structural disorder leads to motifs that are similar to those observed in MgNi 3 B 2 and other related ternary borides, no evidence of an ordered superstructure was found by single-crystal X-ray diffraction or high-resolution powder X-ray diffraction. In the case of CeCo 3 B 2 , boron atoms occupy the center of regular Co 6 trigonal prisms; in MgCo 3 B 2 , boron atoms are shifted from the center of the prism to form B–B dimers with roughly the same length as those found in MgNi 3 B 2 . Magnetic susceptibility data exhibit an unusual temperature dependence that cannot be convincingly modeled by the modified Curie–Weiss equation, consistent with DFT calculations predicting a nonmagnetic ground state. Intrinsic susceptibility at 300 K is 1.42 × 10 –3 emu/mol Oe, which is comparable to that of paramagnetic YCo 3 B 2 and CeCo 3 B 2 with a similar structure and composition. Here, this study showcases the efficacy of combining several methodologies to discover new solids in unexplored phase spaces. This approach includes in situ PXRD data to monitor reactions of precursors upon heating, a diffusion-enhanced synthesis method, and DFT assessment of compound stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Insights into Molecular Magnetism in Metal–Metal Bonded Systems as Revealed by a Spectroscopic and Computational Analysis of Diiron Complexes

A pair of bimetallic compounds featuring Fe–Fe bonds, [Fe( i PrNPPh 2 ) 3 FeR] (R = PMe 3 , ≡N t Bu), have been investigated using High-Frequency Electron Paramagnetic Resonance (HFEPR) as well as field- and temperature-dependent 57 Fe nuclear γ resonance (Mössbauer) spectroscopy. To gain insight into the local site electronic structure, we have concurrently studied a compound containing a single Fe(II) in a geometry analogous to that of one of the dimer sites. Our spectroscopic studies have allowed for the assessment of the electronic structure via the determination of the zero-field splitting and 57 Fe hyperfine parameters for the entire series. We also report on our efforts to correlate structure with physical properties in metal–metal bonded systems using ligand field theory guided by quantum chemical calculations. Through the insight gained in this study, we discuss strategies for the design of single-molecule magnets based on polymetallic compounds linked via direct metal–metal bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Homoleptic Uranium–Bis(acyl)phosphide Complexes

Here, the first uranium bis(acyl)phosphide (BAP) complexes were synthesized from the reaction between sodium bis(mesitoyl)phosphide (Na( mes BAP)) or sodium bis(2,4,6-triisopropylbenzoyl)phosphide (Na( tripp BAP)) and UI 3 (1,4-dioxane) 1.5 . Thermally stable, homoleptic BAP complexes were characterized by single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy, when appropriate, for the elucidation of the electronic structure and bonding of these complexes. EPR spectroscopy revealed that the BAP ligands on the uranium center retain a significant amount of electron density. The EPR spectrum of the trivalent U( tripp BAP) 3 has a rhombic signal near g = 2 (g 1 = 2.03; g 2 = 2.01; and g 3 = 1.98) that is consistent with the EPR-observed unpaired electron being located in a molecular orbital that appears ligand-derived. However, upon warming the complex to room temperature, no resonance was observed, indicating the presence of uranium character.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Radiation Effects on Uranyl Tetrachloro Coordination Compounds: Impact of Lattice Water

Nuclear materials, such as uranium-bearing solids, are exposed to high levels of ionizing radiation throughout the nuclear fuel cycle; thus, it is important to develop a molecular-level understanding of how these materials behave and degrade in the presence of gamma (γ) irradiation. In the current study, three U(VI) tetrachloride complexes, M 2 [UO 2 Cl 4 ]·xH 2 O (where M = K + , Rb + , or Cs + and x = 0 or 2), and their respective chloride salts were exposed to 1–50 kGy of γ radiation using a 60 Co source. Irradiated materials were evaluated by using electron paramagnetic resonance (EPR) and Raman spectroscopy and were further explored by using density functional theory (DFT) methods. EPR spectra of the irradiated materials suggest the formation of a Cl-based radical for both the alkali salts and the uranyl tetrachloride compounds, and DFT calculations provide evidence that the Cl 2 –• radical is formed within these materials. The presence of water in the K + and Rb + compounds leads to additional spectroscopic signatures that could be traced back to water radiolysis and the formation of peroxide and superoxide species. DFT results support the formation of HO 2 • in the lattice and potentially the formation of a [UO 2 Cl 3 (O 2 )] 3– species, highlighting the impact of water within the hydrated material to alter U(VI) speciation by radiolysis.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Magnetic and EPR Spectroscopic Studies of Thiolate Bridged Divalent Ni, Pd, and Pt Ions Capped with VO(N 2 S 2 ) Metalloligands

Reactions of the metallodithiolate complex VO(bme-dach) (hereafter abbreviated as V, where bme-dach = N,N ′-bis(2-mercaptoethyl)-1,4-diazacycloheptane) with [Pd II (CH 3 CN) 4 ](BF 4 ) 2 and [Pt II (CH 3 CN) 4 ](BF 4 ) 2 yield the V–M–V trimetallic compounds [VPdV](BF 4 ) 2 (2) and [VPtV](BF 4 ) 2 (3). Reaction of a similar metalloligand, VO(bme-daco) (hereafter abbreviated as V′ where bme-daco = N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane) with [Ni II (CH 3 CN) 6 ](BF 4 ) 2 afforded the related salt [V′NiV′](BF 4 ) 2 (1). X-ray structural analyses revealed that cations in 1, 2, and 3 adopt a stairstep C 2h structure consisting of two terminal VO(N 2 S 2 ) moieties bridged via thiolate sulfur to the group 10 metal ions. Weak ferromagnetic superexchange coupling (J = 0.282 cm –1 for 1, 0.954 cm –1 for 2, and 1.372 cm –1 for 3) was observed between the two S = 1/2 V IV centers separated by distances in the range of 5.9–6.3 Å, with J values varying following the order Ni < Pd < Pt. Frozen-solution EPR spectra measured on the more soluble [BArF 24 ] − (BArF 24 – = tetrakis((3,5-trifluoromethyl)phenyl)borate) analogues revealed that the [VPtV] 2+ cation exhibits a 15-line hyperfine splitting of 225 MHz at g = 4 in parallel mode, confirming exchange coupling between the two 51 V, I = 7/2 nuclei. Density-functional theory (DFT) calculations indicate an S = 1 ground state for 1–3. These results demonstrate that the choice of paramagnetic metallodithiolate ligand and diamagnetic bridge in such trimetallic species influences the sign and magnitude of magnetic interactions.

anions↗

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 OSTI2024

Cu(II) Stability and UV-Induced Electron Transfer in a Metal–Organic Hybrid: An EPR, DFT, and Crystallographic Characterization of Copper-Doped Zinc Creatininium Sulfate

Single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopic experiments, complemented by quantum chemical DFT calculations, were carried out on the copper-doped metal–organic hybrid and Tutton salt analogue zinc creatininium sulfate to determine its crystal structure, to characterize the electronic structure of the doped Cu(II) binding site, and to propose a pathway for an excited-state, proton-coupled electron transfer (PCET) process in UV-exposed crystals. The crystal structure is isomorphous to that of cadmium creatininium sulfate, which has the transition ion, not in direct coordination with the creatinine, but forming a hexahydrate complex, which is bridged to a creatininium through an intervening sulfate ion. The EPR g (2.446, 2.112, 2.082) and copper hyperfine (A Cu : -327, -59.6, 10.8 MHz) tensor parameters are consistent with doped copper replacing host zinc in the metal–hexahydrate complex. These parameters are similar to those observed for copper hexahydrate in doped Tutton salt systems at low temperature, where the unpaired electron occupies mainly the copper 3d x 2 –y 2 orbital. At room temperature in the Tutton systems, vibration couplings stemming from a dynamic Jahn–Teller effect cause tensor averaging which results in a reduction in their maximum g-tensor and hyperfine tensor values. However, like for the doped isomorphous Cd creatinine crystal, the Cu(II) EPR exhibits little, or no room temperature averaging compared to its low temperature pattern. Samples exposed to 254 nm UV light generate a carbon-centered free radical species, characterized by an isotropic g-tensor (g = 2.0029) and an alpha-proton hyperfine coupling (-24 -14 +4 G). These parameters identify it as a creatinine radical cation formed by the oxidative release of one of its C2 methylene hydrogens. DFT calculations confirm the unpaired electronic structures of both the Cu(II) site and free radical. The growth in radical concentration with an increase in the UV exposure time coincides with a decrease in the copper EPR signal, indicating a coupled light-induced oxidation reduction process. A comparison of the crystal structure with the EPR parameters and DFT results provides evidence for a UV-induced PCET.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Evolution of Radicals from the Photolysis of High Ionic Strength Alkaline Nitrite Solutions

Reactive nitrogen species (RNS), along with reactive oxygen species (ROS), are significant products from radiolysis in solution. While much research has been focused on biological systems, these species are also important products in the autoradiolysis that occurs in nuclear waste. In this work, we determine the correlation between solution constituents, particularly nitrite, and radical products in highly alkaline solutions relevant to liquid waste. Because these radicals tend to be very short-lived, we employ spin trapping in conjunction with electron paramagnetic resonance (EPR) to detect them and quantify their production. Most spin traps do not function in these conditions (>1 M NaOH); however, nitroalkanes such as nitromethane will act as spin traps in their aci form, which is dominant at high pH. To restrict the products to those originating from nitrite, we use 280–480 nm UV light to generate radicals, avoiding products from the photolysis of water. Under these circumstances, nitric oxide, nitrite radicals, and hydroxyl radicals are detected, and the trends with the concentration of the constituents of the solutions are tracked. These include nitrite, nitrate, hydroxide, and carbonate. We find that, while the equilibrium shifts with increasing pH from hydroxyl radicals to the more slowly reacting oxide radicals, the production of nitrite radicals does not decrease.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗