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At least 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Electrochemical characterization of B-site cation-excess Pr 2 Ni 0.75 Cu 0.25 Ga 0.05 O 4+δ cathode for IT-SOFCs

In this paper, the B-site cation-excess K 2 NiF 4 -type structure oxide, Pr 2 Ni 0.75 Cu 0.25 Ga 0.05 O 4+δ (PNCG) is investigated as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). XRD result shows that PNCG cathode is chemically compatible with the electrolyte Gd 0.1 Ce 0.9 O 2-δ (GDC) at 900 °C for 5 h. The PNCG material exhibits a semiconductor to metal transition around 425 °C. The thermal expansion coefficient (TEC) of the PNCG sample is 12.72×10 -6 K -1 between 30 and 850 °C in air. The polarization resistance (R p ) of PNCG cathode on GDC electrolyte is 0.105, 0.197 and 0.300 Ω cm 2 at 800, 750, 700 °C, respectively. A maximum power density of 371 mW cm -2 is obtained at 800 °C for single-cell with 300 μm thick GDC electrolyte and PNCG cathode. Finally, the results of this study demonstrate that PNCG can be a promising cathode material for IT-SOFCs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effect of metal fluorides on the corrosion of structural materials in molten LiF-NaF-KF

The corrosion of structural materials in molten fluoride salts is predominantly caused by the presence of impurities in the salt. Here, this study focuses on understanding the corrosion behavior of selected alloys in molten FLiNaK salt with addition of similar quantities of metal fluoride impurities such as CrF 2 , CrF 3 , FeF 2 , FeF 3 , and NiF 2 . The results show that the presence of selected metal fluoride impurities increases the extent of corrosion of the selected alloys in molten FLiNaK salt, with the exact effect depending on the thermodynamic stability of the fluoride impurity added as well as the composition of the structural alloy studied.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Split radiographic tracer technique to measure the full width of a high energy density mixing layer

In this work, we describe a new radiography–based technique for measuring the width of the mixing layer that develops when high–energy–density (HED) fluids of different density mix at an interface. In a traditional radiography target, the denser material includes an embedded, density–matched, high opacity, tracer layer to focus the radiograph on a 2D slice of the 3D flow field. The high opacity layer enhances the contrast between the dense and light materials that permits a clear identification of the spike front, i.e. penetration of the dense material into the light material, but obscures the bubble front, i.e. penetration of the light material into the heavy when the fluids are highly interpenetrated, as in a turbulent mixing layer. On the other hand, removing the tracer layer makes it difficult to identify the interface at all, due to poor contrast and an increased susceptibility to edge effects. Our solution is a split tracer approach where half the target uses the traditional geometry while the other half utilizes a special tracer layer in the light material to produce a radiograph with inverse x-ray opacity characteristics when backlit at a specified x–ray energy. Hydrodynamic equivalency is maintained between the two halves of the target. By making a single target with the traditional and inverse material pairs set side-by-side, we are able to simultaneously measure the penetration of bubbles and spikes in a deeply nonlinear flow, yielding the full mix width. We discuss this new target concept and present our first experiments at the National Ignition Facility (NIF) demonstrating the viability of this technique.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Recent and planned hydrodynamic instability experiments on indirect-drive implosions on the National Ignition Facility

At National Ignition Facility (NIF), yield amplification due to alpha particle heating approached ~3 in the highest performing inertial confinement fusion (ICF) implosions, while yield amplification of ~15-30 is needed for ignition. Hydrodynamic instabilities are a major factor in degradation of implosions while understanding and mitigation of the instabilities are critical to achieving ignition. This article describes recent and planned hydrodynamic instability experiments with several focused platforms that have been developed to directly measure these instabilities in all phases of ICF implosions. Measurements of ripple-shock generation at OMEGA laser have indicated initial seeds for the instabilities in three ablators - plastic (CH), beryllium, and high-density carbon (HDC). Hydrodynamic Growth Radiography (HGR) platform was used to measure instability growth at the ablation front in the acceleration phase of implosions. This platform used pre-imposed 2-D perturbations for growth factor measurements at different perturbation wavelengths and was also used to measure growth of “native roughness” modulations, fill tubes, and capsule support membranes or “tents”. Also, in the acceleration phase several new experimental platforms have been or are being developed to measure instability growth at the ablator-ice interface. In the deceleration phase of implosions, “self-emission” and “self-backlighting” platforms were developed to measure perturbations near peak compression. This article reviews recent progress and results.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Probing dense plasmas for HEDS and ICF*

This paper is a retrospective of almost four decades of conceptualization and development of active x-ray probing of dense plasmas, involving multiple teams. In hindsight it was a surprisingly nonlinear and nonsystematic progression, with cycles of key epiphanies followed by multi-step technique optimization, spanning years.Further, each new idea or endeavor, whether or not realized / successful, spawned the next, and not necessarily in order of difficulty. The journey can be summarized by adapting/paraphrasing what Edward Teller said about NIF, that we develop new capabilities precisely because we don't know what those capabilities will enable.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Use of tritium-rich fuel to improve the yield of layered deuterium/tritium inertial fusion capsules

In deuterium–tritium (DT) ice layered implosions, nearly all hot spot mass at peak burn comes from the dense fuel. Accurate prediction of the fuel mass ablation, including the enthalpy associated with mass inflow into the hot spot from the dense fuel, is essential to understanding the energetics and ignition of the hot spot in layered implosions. A recently published boundary layer analysis (Daughton et al., 2023) indicates a faster mass ablation rate than in previous analyses of layered implosions. Inclusion of this effect provides a better match to simulations and leads to a new ignition threshold where the temperature of the dense fuel plays a critical role. This analysis motivates possible new directions for improved capsule performance. Here, the authors present evidence in support of one such approach: the use of tritium-rich ice to decrease 14 MeV neutron scattering and heating of the dense fuel, resulting in less mass ablation and more robust burn of the hot spot. It is found from numerical simulations that despite a less favorable D:T ratio in the ice, the use of a 40:60 D:T ratio leads to an increase in capsule yield of 17% percent compared with that of a 50:50 D:T ratio fuel for capsules resembling those of the recent N210808 ignition experiment on the NIF (Abu-Shawareb et al., 2022) and an increase of 74% compared with that of a 60:40 D:T ratio fuel capsule. Finally, these results are potentially important for modeling all layered implosions, since some degree of DT fractionization may arise naturally during the beta layering process. In addition, this physics is important for the feasibility of high-gain capsule designs that seek to minimize tritium usage, as in some inertial fusion energy concepts.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Overview of oxygen opacity experiments at the National Ignition Facility and investigation of potential systematic errors

Experiments to measure oxygen opacity at stellar interior conditions have been performed at the National Ignition Facility in a Discovery Science campaign. These experiments utilize the Opacity-on-NIF platform with a sample comprised of O, Mg, and Si. The spectral data from the Opacity Spectrometer cover the 1000–2000 eV photon energy range showing bound-free continuum absorption from O and line absorption from Mg and Si. DANTE and the Gated X-ray Detector are employed to measure the sample plasma’s temperature and density, respectively. Initial data show lower transmission than expected by theoretical models, raising questions of whether potential background or data uniformity concerns could produce systematic errors in the inferred transmission. Here, we investigate three concerns thought to be important for the oxygen opacity data, including instrumental scattered background, sample self-emission non-uniformity, and backlight continuum non-uniformity. Additionally, we show the effect of a recently developed method to account for 2nd order crystal reflection. The total effect of these concerns on one experiment is found to be small compared to the observed difference between the inferred transmission and a model calculation at the inferred temperature and density. Thus, we conclude that these potential sources of systematic error cannot account for the observed difference, increasing the likelihood of a real effect due to the high temperature and density conditions. However, because this is only a single experiment, we cannot make a firm conclusion. More experiments measuring the opacity and necessary calibrations are needed to assess the reproducibility and uncertainty of this result.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Influences of shock imprinting on mix in a 3D-printed porous media

Mixing of materials in porous media can cause a significant impact on fusion yield as previously demonstrated by the National Ignition Facility (NIF) MARBLE Campaign. Initially, the reactants are separated, with deuterium in the lattice struts and a tritium gas fill in the voids. Lattice parameters such as the strut thickness and relative pitch, provide a control for the mix parameters in the experiment. Los Alamos National Laboratory’s (LANL) BOSQUE project looks to better understand how the mix of the reactants and shell materials impact the fusion burn and resultant yield on various laser platforms. xRAGE’s Eulerian hydrodynamics and adaptive mesh refinement (AMR) provide the unique ability to study the impacts of multiscale features of complex lattice structures. This modeling provides the ability to measure shock front variations as the wave progress’ through a given media. Initial conditions of the lattice are essential to accurately model mix and burn measured by experiment. By varying the initial orientation and densities of these lattice regions the early time dynamics of how the shock is launched into the system is changed and advocates for the study of resulting effects. In this work, we will study the sensitivities of shock effects in varying 3D printed geometric systems and how these shocks alter the structure and mix in the lattice. We will discuss both preliminary experimental results and simulations to help plan and constrain future experiments where we will study the impact of different lattice geometries and lattice bulk densities. This work concludes with the relative impacts of lattice geometries on shock speeds at different bulk densities and the resultant mix widths due to those shock interactions. We see agreement with theory at the higher end of our bulk density study, however, as we approach lower bulk density systems the dynamics of these interactions begin to change.

2 Photon Polymerization↗
DOE OSTI2013

Synthesis, magnetic and electric transport properties of mixed-valence manganites La{sub 0.5+x}Sr{sub 1.5−x}Mn{sub 0.5}Cr{sub 0.5}O{sub 4} (x=0.1, 0.2 and 0.3)

A series of mixed-valence manganites La{sub 0.5+x}Sr{sub 1.5−x}Mn{sub 0.5}Cr{sub 0.5}O{sub 4} were synthesized by sol–gel method. Rietveld profile analysis shows that the phases crystallize with tetragonal unit cell in the space group I4/mmm. The lattice parameter c increases with increase in x while a parameter almost remains constant. The Weiss constant (θ) is positive for all the phases and found to increase with increase in x. The ferromagnetic interactions becomes more dominant with increase in x due to increase in Mn{sup 3+}–O–Mn{sup 4+} and Mn{sup 3+}–O–Cr{sup 3+} double exchange interactions. Resistivity can be described by the polaron hopping and the variable range hopping model. It was found that the transport mechanism is dominated by Mott's variable range hopping (VRH) model with a decrease of Mott localization energy with increase in x, which explains the decrease of resistivity. - Graphical abstract: Unit cell structure of La{sub 0.6}Sr{sub 1.4}Mn{sub 0.5}Cr{sub 0.5}O{sub 4}. Display Omitted Research highlights: • A series of K{sub 2}NiF{sub 4}-type compounds La{sub 0.5}+xSr{sub 1.5-x}Mn{sub 0.5}Cr{sub 0.5}O{sub 4} (x=0.1, 0.2, 0.3) have been synthesized. • The calculated tolerance factors confirms the tetragonal symmetry of the proposed phases. • The lattice parameter c increases with increase in x while a parameter almost remains constant. • The Weiss constant (θ) is positive for all the phases and found to increase with increase in x • The resistivity data has been best fitted using the Mott's variable range hopping (VRH) model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Chemical compatibility study of melilite-type gallate solid electrolyte with different cathode materials

Chemical reactivity between cathodes and electrolytes is a crucial issue for long term SOFCs stability and performances. In this study, chemical reactivity between selected cathodic materials and the ionic conducting melilite La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25} has been extensively investigated by X-ray powder diffraction in a wide temperature range (up to 1573 K). Perovskite-type La{sub 0.8}Sr{sub 0.2}MnO{sub 3−d} and La{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−d} and K{sub 2}NiF{sub 4}-type La{sub 2}NiO{sub 4+d} were selected as cathode materials. The results of this study allow identifying the most suitable electrode material to be used in combination with the melilite-type gallate electrolyte and set the basis for future work on this novel system. - Graphical abstract: Chemical reactivity between cathodes and electrolytes is a crucial issue for long term SOFCs stability and performances. In this study, chemical reactivity between selected cathodic materials and the ionic conducting melilite La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25} has been extensively investigated by means of X-ray powder diffraction. - Highlights: • Chemical compatibility between melilite-type gallate and cathodes for SOFCs up to 1573 K. • No reactivity observed between La{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}. • Reactivity observed between La{sub 0.80}Sr{sub 0.20}MnO{sub 3−d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}. • Significant reactivity observed between La{sub 2}NiO{sub 4+d} and La{sub 1.50}Sr{sub 0.50}Ga{sub 3}O{sub 7.25}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Chemical and structural changes in Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) lanthanide nickelates as a function of oxygen partial pressure at high temperature

The chemical stability of lanthanide nickelates Ln{sub 2}NiO{sub 4+δ} (Ln=La, Pr or Nd) has been studied in the temperature range 25–1300 °C, either in air or at low pO{sub 2} (down to 10{sup −4} atm). Thermal gravimetry analysis (TGA) measurements coupled with X-ray diffraction (XRD) characterization have shown that all compounds retain their K{sub 2}NiF{sub 4}-type structure in these conditions, while remaining over-stoichiometric in oxygen up to 1000 °C. Only Nd{sub 2}NiO{sub 4+δ} starts to decompose into Nd{sub 2}O{sub 3} and NiO above 1000 °C, at pO{sub 2}=10{sup −4} atm. In addition, a careful analysis of the lanthanide nickelates structural features has been performed by in situ XRD, as a function of temperature and pO{sub 2}. For all compounds, a structural transition has been always observed in the temperature range 200–400 °C, in air or at pO{sub 2}=10{sup −4} atm. In addition, their cell volume did not vary upon the variation of the oxygen partial pressure. Therefore, these materials do not exhibit a chemical expansion in these conditions, which is beneficial for a fuel cell application as cathode layers. Additional dilatometry measurements have revealed that a temperature as high as 950 °C for Pr{sub 2}NiO{sub 4+δ} or 1100 °C for La{sub 2}NiO{sub 4+δ} and Nd{sub 2}NiO{sub 4+δ} has to be reached in order to begin the sintering of the material particles, which is of primary importance to obtain an efficient electronic/ionic conduction in the corresponding designed cathode layers. Besides, excellent matching was found between the thermal expansion coefficients of lanthanide nickelates and SOFC electrolytes such as 8wt% yttria stabilized zirconia (8YSZ) or Ce{sub 0.8}Gd{sub 0.2}O{sub 2−δ} (GDC), at least from 400 °C up to 1400 °C in air or up to 1200 °C at pO{sub 2}=10{sup −4} atm. - Graphical abstract: This study reports the good chemical stability of oxygen overstoichiometric Ln2NiO4+δ(Ln = La, Pr or Nd) at high temperatures (up to 1300 °C), eitherin air or at pO2down to 10-4 atm. In addition, these MSC cathode materials show a small chemical expansion as well as a good TEC compatibility with electrolyte materials (GDC or YSZ). - Highlights: • The structure of Ln2NiO4+δ compounds are studied vs. temperature and pO2 • Structural transitions are evidenced in air as well as in low pO2 atmosphere • The structural transitions do not significantly affect their TECs values • Up to 1200 °C, they show good chemical stability and no chemical expansion vs. pO2 • TECs of nickelates, 8YSZ and GDC are compared in air and in low pO2 atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Phase equilibria, crystal structure and properties of complex oxides in the Nd{sub 2}O{sub 3}–SrO–CoO system

The phase equilibria in the ½Nd{sub 2}O{sub 3}–SrO–CoO system were systematically studied at 1373 K in air. The intermediate phases formed in the ½Nd{sub 2}O{sub 3}–SrO–CoO system at 1373 K in air are: Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} (0.0≤x≤0.5 with orthorhombic structure, sp. gr. Pbnm and 0.6≤x≤0.95 whose structure was detected as cubic according to XRD sp. gr. Pm3m, but shown to be tetragonal by TEM due to the oxygen vacancy ordering), Nd{sub 2-y}Sr{sub y}CoO{sub 4-δ} (0.6≤y≤1.1 with tetragonal K{sub 2}NiF{sub 4}-type structure, sp. gr. I4/mmm) and Nd{sub 2-z}Sr{sub z}O{sub 3} (0.0≤z≤0.15 with hexagonal structure, sp. gr. P-3m1). The unit cell parameters for the single phase samples were refined by the Rietveld analysis. The changes of oxygen content in Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} (0.6≤x≤0.95) and Ruddlesden-Popper oxide Nd{sub 2-y}Sr{sub y}CoO{sub 4-δ} were examined by TGA. All were found to be oxygen deficient phases. High-temperature dilatometry allows calculating the thermal expansion coefficient and evaluating the chemical expansion coefficient at high temperature. The projection of isothermal-isobaric phase diagram for the Nd–Sr–Co–O system at 1373 K in air to the compositional triangle of metallic components has been constructed. The phase equilibria in the studied Nd–Sr–Co–O system were compared to La–Sr–Co–O and Nd–M–Co–O (M=Ca and Ba). - Graphical abstract: Crystal structure of vacancy ordered supercell for Nd{sub 0.2}Sr{sub 0.8}CoO{sub 3-δ} and projection of phase diagram for the Nd–Sr–Co–O system onto the triangle edge of metallic components at 1373 K in air. - Highlights: • The diagram for the Nd–Sr–Co–O system at 1373 K in air has been constructed. • The crystal structure of Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} and Nd{sub 2-y}Sr{sub y}CoO{sub 4±δ} was refined. • The formation of superstructure due to the oxygen vacancy ordering was proved. • The changes of oxygen content in Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} and Nd{sub 2-y}Sr{sub y}CoO{sub 4±δ} were examined. • Thermal expansion and chemical expansion for Nd{sub 1-x}Sr{sub x}CoO{sub 3-δ} were evaluated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis and structure of a new layered oxyfluoride Sr{sub 2}ScO{sub 3}F with photocatalytic property

Highlights: • A new oxyfluoride compound Sr{sub 2}ScO{sub 3}F was prepared by a solid state route. • The structure of this compound was determined by GSAS program based on XRD data. • The photocatalytic property was investigated under UV irradiation. - Abstract: A new Ruddlesden–Popper type scandium oxyfluoride, Sr{sub 2}ScO{sub 3}F, was synthesized by a conventional solid state reaction route. The detailed structure of Sr{sub 2}ScO{sub 3}F was investigated using X-ray diffraction (XRD) and selected area electron diffraction (SAED). The disorder distribution pattern of fluorine anions was determined by the {sup 19}F nuclear magnetic resonance (NMR) spectrum. The compound crystallizes in a K{sub 2}NiF{sub 4}-type tetragonal structure (space group I4/mmm) with O/F anions disordered over the apical sites of the perovskite-type Sc(O,F){sub 6} octahedron layers interleaved with strontium cations. Ultraviolet–visible (UV–vis) diffuse reflection spectrum of the prepared Sr{sub 2}ScO{sub 3}F indicates that it has an absorption in the UV–vis region. The photocatalytic activity of Sr{sub 2}ScO{sub 3}F was further investigated, showing an effective photodegradation of Rhodamine-B (RB) within 2 h under UV light irradiation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Recent progress on coarse graining simulations

We focus on coarse graining simulations based on the primary conservation equations, effectively codesigned physics and algorithms, and low-Mach-number corrected (LMC) hydrodynamics. Simulation methods involve LANL’s x-Radiation-Adaptive-Grid-Eulerian Large-Eddy Simulation, Besnard-Harlow-Rauenzahn (BHR) Reynolds-Averaged Navier-Stokes (RANS) approach, and Dynamic BHR – a paradigm bridging RANS and LES. A relevant question addressed relates to whether 3D RANS and RANS/LES hybrids – the industry standards for aerospace and automotive research, are presently relevant for practical variable-density applications involving shocked and accelerated interface instabilities. Furthermore, recent simulations of the GaTECH inclined mixing-layer shock-tube and NIF ICF-capsule experiments are used to demonstrate issues, challenges, and potential for 3D coarse grained LMC simulation strategies for robustly simulating complex transitional and coupled hydrodynamics-multiphysics with coarser resolution. Present LES readiness to provide accurate predictions at scale is demonstrated – whereas 3D RANS and RANS/LES bridging do not appear impactful in this context.

42 ENGINEERING↗
DOE OSTI2015

Hydrodynamic instability experiments with three-dimensional modulations at the National Ignition Facility

The first hydrodynamic instability growth measurements with three-dimensional (3D) surface-roughness modulations were performed on CH shell spherical implosions at the National Ignition Facility (NIF) [G. H. Miller, E. I. Moses, and C. R. Wuest, Opt. Eng. 43, 2841 (2004)]. The initial capsule outer-surface amplitudes were increased approximately four times, compared with the standard specifications, to increase the signal-to-noise ratio, helping to qualify a technique for measuring small 3D modulations. The instability growth measurements were performed using x-ray through-foil radiography based on time-resolved pinhole imaging. Averaging over 15 similar images significantly increased the signal-to-noise ratio, making possible a comparison with 3D simulations. At a convergence ratio of ~2.4, the measured modulation levels were ~3 times larger than those simulated based on the growth of the known imposed initial surface modulations. Several hypotheses are discussed, including increased instability growth due to modulations of the oxygen content in the bulk of the capsule. In conclusion, future experiments will be focused on measurements with standard 3D ‘native-roughness’ capsules as well as with deliberately imposed oxygen modulations.

42 ENGINEERING↗
DOE OSTI2022

Tunable Orbital Ferromagnetism at Noninteger Filling of a Moiré Superlattice

Here, the flat bands resulting from moiré superlattices exhibit fascinating correlated electron phenomena such as correlated insulators, ( Nature 2018, 556 (7699), 80–84), ( Nature Physics 2019, 15 (3), 237) superconductivity, ( Nature 2018, 556 (7699), 43–50), ( Nature 2019, 572 (7768), 215–219) and orbital magnetism. ( Science 2019, 365 (6453), 605–608), ( Nature 2020, 579 (7797), 56–61), ( Science 2020, 367 (6480), 900–903) Such magnetism has been observed only at particular integer multiples of n 0 , the density corresponding to one electron per moiré superlattice unit cell. Here, we report the experimental observation of ferromagnetism at noninteger filling (NIF) of a flat Chern band in a ABC-TLG/hBN moiré superlattice. This state exhibits prominent ferromagnetic hysteresis behavior with large anomalous Hall resistivity in a broad region of densities centered in the valence miniband at n = -2.3n 0 . We observe that, not only the magnitude of the anomalous Hall signal, but also the sign of the hysteretic ferromagnetic response can be modulated by tuning the carrier density and displacement field. Rotating the sample in a fixed magnetic field demonstrates that the ferromagnetism is highly anisotropic and likely purely orbital in character.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Implications of bond disorder in a S=1 kagome lattice

Strong hydrogen bonds such as F···H···F offer new strategies to fabricate molecular architectures exhibiting novel structures and properties. Along these lines and, to potentially realize hydrogen-bond mediated superexchange interactions in a frustrated material, we synthesized [H 2 F] 2 [Ni 3 F 6 (Fpy) 12 ][SbF 6 ] 2 (Fpy = 3-fluoropyridine). It was found that positionally-disordered H 2 F + ions link neutral NiF 2 (Fpy) 4 moieties into a kagome lattice with perfect 3-fold rotational symmetry. Detailed magnetic investigations combined with density-functional theory (DFT) revealed weak antiferromagnetic interactions (J ~ 0.4 K) and a large positive-D of 8.3 K with m s = 0 lying below m s = ±1. The observed weak magnetic coupling is attributed to bond-disorder of the H 2 F + ions which leads to disrupted Ni-F···H-F-H···F-Ni exchange pathways. Despite this result, we argue that networks such as this may be a way forward in designing tunable materials with varying degrees of frustration.

Science & Technology - Other Topics↗
DOE OSTI2023

Scrutinizing formally Ni IV centers through the lenses of core spectroscopy, molecular orbital theory, and valence bond theory

Nickel K- and L 2,3 -edge X-ray absorption spectra (XAS) are discussed for 16 complexes and complex ions with nickel centers spanning a range of formal oxidation states from II to IV. K-edge XAS alone is shown to be an ambiguous metric of physical oxidation state for these Ni complexes. Meanwhile, L 2,3 -edge XAS reveals that the physical d-counts of the formally Ni IV compounds measured lie well above the d 6 count implied by the oxidation state formalism. The generality of this phenomenon is explored computationally by scrutinizing 8 additional complexes. The extreme case of NiF 6 2- is considered using high-level molecular orbital approaches as well as advanced valence bond methods. The emergent electronic structure picture reveals that even highly electronegative F-donors are incapable of supporting a physical d 6 Ni IV center. The reactivity of Ni IV complexes is then discussed, highlighting the dominant role of the ligands in this chemistry over that of the metal centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗