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

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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Haldane topological spin-1 chains in a planar metal-organic framework

Haldane topological materials contain unique antiferromagnetic chains with symmetry-protected energy gaps. Such materials have potential applications in spintronics and future quantum computers. Haldane topological solids typically consist of spin-1 chains embedded in extended three-dimensional (3D) crystal structures. Here, we demonstrate that [Ni(μ-4,4'-bipyridine)(μ-oxalate)] n (NiBO) instead adopts a two-dimensional (2D) metal-organic framework (MOF) structure of Ni 2+ spin-1 chains weakly linked by 4,4'-bipyridine. NiBO exhibits Haldane topological properties with a gap between the singlet ground state and the triplet excited state. The latter is split by weak axial and rhombic anisotropies. Several experimental probes, including single-crystal X-ray diffraction, variable-temperature powder neutron diffraction (VT-PND), VT inelastic neutron scattering (VT-INS), DC susceptibility and specific heat measurements, high-field electron spin resonance, and unbiased quantum Monte Carlo simulations, provide a detailed, comprehensive characterization of NiBO. Vibrational (also known as phonon) properties of NiBO have been probed by INS and density-functional theory (DFT) calculations, indicating the absence of phonons near magnetic excitations in NiBO, suppressing spin-phonon coupling. The work here demonstrates that NiBO is indeed a rare 2D-MOF Haldane topological material.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Intensification of future subsurface marine heatwaves in an eddy-resolving model

A shift in depth range enables marine organisms to adapt to marine heatwaves (MHWs). Subsurface MHWs could limit this pathway, yet their response to climate warming remains unclear. Here, using an eddy-resolving Earth system model forced under a high emission scenario, we project a robust global increase in subsurface MHWs driven by rising subsurface mean temperatures and enhanced temperature variability. Historically, maximum MHW intensity occurs around 100m depth, which shifts to the faster-warming surface under greenhouse warming. However, removing the long-term warming trend yields an increase in subsurface MHW intensity and annual days greater than that at the surface, especially in large marine ecosystem regions, primarily due to increased variability. Additionally, days of the surface and subsurface concurrent event increase ten times more than those of individual events. Our study highlights a heightened threat to marine organisms under global warming, as the increased subsurface heatwaves reduce their refuge options.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Tunable quadruple-well ferroelectric van der Waals crystals

The family of layered thio- and seleno-phosphates has gained attention as potential control dielectrics for the rapidly growing family of two-dimensional and quasi-two-dimensional electronic materials. Here we report a combination of density functional theory calculations, quantum molecular dynamics simulations and variable-temperature, -pressure and -bias piezoresponse force microscopy data to predict and verify the existence of an unusual ferroelectric property—a uniaxial quadruple potential well for Cu displacements—enabled by the van der Waals gap in copper indium thiophosphate (CuInP 2 S 6 ). The calculated potential energy landscape for Cu displacements is strongly influenced by strain, accounting for the origin of the negative piezoelectric coefficient and rendering CuInP 2 S 6 a rare example of a uniaxial multi-well ferroelectric. Experimental data verify the coexistence of four polarization states and explore the temperature-, pressure- and bias-dependent piezoelectric and ferroelectric properties, which are supported by bias-dependent molecular dynamics simulations. As a result, these phenomena offer new opportunities for both fundamental studies and applications in data storage and electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Local lattice distortions drive the transition of BaIrO 3 into a ferromagnetic insulator state

Using variable temperature total and resonant x-ray scattering at the K edge of Ir species, we study the “bad metal” to insulator transition in BaIrO 3 , a canonical third transition series oxide. The usage of advanced experimental techniques and large-scale computer modeling helps us show that, contrary to the widely accepted view, charge disproportionation leading to the formation of Ir-trimers with a different number of 5d valence electrons already exists at room temperature. The charge disbalance between the trimers does not evolve much with decreasing temperature while local lattice distortions do, suggesting that the latter and not the former make a key contribution to the emergence of the enigmatic ferromagnetic insulator state of BaIrO 3 . The conclusion is supported by DFT calculations based on unmodified experimental structure data. Our work calls for a reconsideration of the role of lattice distortions in determining the electronic properties of third transition series oxides. It also charts a path to assessing these properties on a realistic and not assumed crystal structure basis.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Coordination and activation of nitrous oxide by iron zeolites

Iron-containing zeolites are heterogeneous catalysts that exhibit remarkable activity in the selective oxidation of inert hydrocarbons and catalytic decomposition of nitrous oxide (N 2 O). The reduction of N 2 O is critical to both these functions, but experimental data tracking the iron active sites during N 2 O binding and activation are limited. Here, the N 2 O-ligated Fe(ii) active site in iron-exchanged zeolite beta is isolated and characterized by variable-temperature Mössbauer, diffuse reflectance UV-vis-NIR and Fourier transform infrared spectroscopy. N 2 O binds through the terminal nitrogen atom with substantial backbonding from the Fe(ii) centre at low temperature. At higher temperatures, the Fe–N 2 O interaction is weakened, facilitating isomerization to the O-bound form, which is competent in O-atom transfer. Density functional theory calculations show the geometric and electronic structure requirements for N 2 O binding and activation. A geometric distortion imposed by the zeolite lattice plays an important role in activating N 2 O. As a result, this highlights a mechanism for structural control over function in Fe-zeolite catalysts.

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

Organogold oligomers: Exploiting iClick and aurophilic cluster formation to prepare solution stable Au 4 repeating units

A novel synthetic method to create gold based metallo–oligomers/polymers via the combination of inorganic click (iClick) with intermolecular aurophilic interactions is demonstrated. Complexes [PEt 3 Au] 4 (μ-N 3 C 2 C 6 H 5 ) (1) and [PPhMe 2 Au] 4 3 C 2 C 6 H 5 ) (2) and {[PEt 3 Au] 4 [(μ-N 3 C 2 ) 2 -9,9-dihexyl-9H-fluorene]} n (8) have been synthesized via iClick. The tetranuclear structures of 1 and 2, induced by aurophilic bonding, are confirmed in the solid state through single crystal X-ray diffraction experiments and in solution via variable temperature NMR spectroscopy. The extended 1D structure of 8 is constructed by aurophilic induced self-assembly. 1 H DOSY NMR analysis reveals that the aurophilic bonds in 1, 2, and 8 are retained in the solution phase. The degree of polymerization within complex 8 is temperature and concentration dependent, as determined by 1 H DOSY NMR. The complex 8 is a rare example of a solution stable higher ordered structure linked by aurophilic interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2016

On the origin of high ionic conductivity in Na-doped SrSiO 3

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29 Si, 23 Na, and 17 O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3 , which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na x Sr 1-x SiO 3-0.5x , and with >10 mol% Na doping, phase separation occurs, leading to the formation of an amorphous phase β-Na 2 Si 2 O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2 Si 2 O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Structural elucidation of a mononuclear titanium methylidene

The first example of a structurally characterized titanium methylidene, (PN) 2 Ti=CH 2 , has been prepared via one-electron oxidation of (PN) 2 Ti(CH 3 ) followed by deprotonation or by H-atom abstraction using an aryloxyl radical. The Ti=C distance was found to be 1.939(3) Å, and variable temperature, multinuclear, and multidimensional NMR spectroscopic experiments revealed the methylidene to engage in long range interactions with protons on the ligand framework. Here, computational studies showed that the Ti=C bond, which until now has eluded structural studies, displays all the hallmarks of a prototypical Schrock-carbene.

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

DNP-enhanced ultrawideline 207 Pb solid-state NMR spectroscopy: an application to cultural heritage science

Dynamic nuclear polarization (DNP) is used to enhance the (ultra)wideline 207 Pb solid-state NMR spectra of lead compounds of relevance in the preservation of cultural heritage objects. The DNP SSNMR experiments enabled, for the first time, the detection of the basic lead carbonate phase of the lead white pigment by 207 Pb SSNMR spectroscopy. Variable-temperature experiments revealed that the short T'2 relaxation time of the basic lead carbonate phase hinders the acquisition of the NMR signal at room temperature. We additionally observe that the DNP enhancement is twice as large for lead palmitate (a lead soap, which is a degradation product implicated in the visible deterioration of lead-based oil paintings), than it is for the basic lead carbonate. As a result, this enhancement has allowed us to detect the formation of a lead soap in an aged paint film by 207 Pb SSNMR spectroscopy; which may aid in the detection of deterioration products in smaller samples removed from works of art.

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

Rapid self-healing and anion selectivity in metallosupramolecular gels assisted by fluorine–fluorine interactions

Simple ML 2 [M = Fe(II), Co(II), Ni(II)] complexes taken from a perfluoroalkylamide derivative of 4-aminophenyl-2,2',6,2'-terpyridine spontaneously, yet anion selectively, self-assemble into gels, which manifest an unprecedented rapid gel strength recovery, viz . self-healing, and thermal rearrangement in aqueous dimethyl sulfoxide. The key factor for gelation and rheological properties emerges from the fluorine–fluorine interactions between the perfluorinated chains, as the corresponding hydrocarbon derivative did not form metallogels. The perfluoro-terpyridine ligand alone formed single crystals, while its Fe(II), Co(II) or Ni(II) complexes underwent rapid gelation leading to highly entangled fibrillar networks visualized by electron microscopy. The thermodynamic parameters of gelation based on variable temperature NMR 1 H and 19 F resonances showed that gelation was enthalpically favourable and entropically disfavourable. The step strain rheological experiments demonstrated that the gels undergo rapid self-healing and the morphological features, thermal stability and mechanical properties were found to depend on the nature of the metal ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Oxygen activation at a dicobalt centre of a dipyridylethane naphthyridine complex

We present that the mechanism of oxygen activation at a dicobalt bis-μ-hydroxo core is probed by the implementation of synthetic methods to isolate reaction intermediates. Reduction of a dicobalt(III,III) core ligated by the polypyridyl ligand dipyridylethane naphthyridine (DPEN) by two electrons and subsequent protonation result in the release of one water moiety to furnish a dicobalt(II,II) center with an open binding site. This reduced core may be independently isolated by chemical reduction. Variable-temperature 1 H NMR and SQUID magnetometry reveal the reduced dicobalt(II,II) intermediate to consist of two low spin Co(II) centers coupled antiferromagnetically. Binding of O 2 to the open coordination site of the dicobalt(II,II) core results in the production of an oxygen adduct, which is proposed to be a dicobalt(III,III) peroxo. Lastly, electrochemical studies show that the addition of two electrons results in cleavage of the O–O bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy

Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L 2,3 -edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine Fe I dopant ions to be linearly coordinated, occupying a D 6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L 2,3 -edge XAS from which the energy reduction of 3d z 2 due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L 3 -edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (~280 cm –1 ), that corresponds with Orbach relaxation via the first excited, M J = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.

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

Metallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer

We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of Y x Sc 3-x N@C 80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S 1 –T 1 gap decrease in this row. For Sc 3 N@C 80 , we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14 N, 45 Sc, and 89 Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y 3 N to Sc 3 N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.

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

Hydrogen bonds and dispersion forces serving as molecular locks for tailored Group 11 bis(amidine) complexes

A flexible polydentate bis(amidine) ligand LH 2 , LH 2 = {CH 2 NH( t Bu)C=N-2-(6-MePy)} 2 , operates as a molecular lock for various coinage metal fragments and forms the dinuclear complexes [LH 2 (MCl) 2 ], M = Cu (1), Au (2), the coordination polymer [{(LH 2 ) 2 (py) 2 (AgCl) 3 }(py) 3 ] n (3), and the dimesityl-digold complex [LH 2 (AuMes) 2 ] (4) by formal insertion of MR fragments (M = Cu, Ag, Au; R = Cl, Mes) into the N–H∙∙∙N hydrogen bonds of LH 2 in yields of 43–95%. Complexes 1, 2, and 4 adopt C 2 -symmetrical structures in the solid state featuring two interconnected 11-membered rings that are locked by two intramolecular N–H∙∙∙R–M hydrogen bonds. QTAIM analyses of the computational geometry-optimized structures 1a, 2a, and 4a reveal 13, 11, and 22 additional bond critical points, respectively, all of which are related to weak intramolecular attractive interactions, predominantly representing dispersion forces, contributing to the conformational stabilization of the C2-symmetrical stereoisomers in the solid state. Variable-temperature 1 H NMR spectroscopy in combination with DFT calculations indicate a dynamic conformational interconversion between two C 2 -symmetrical ground state structures in solution (ΔG ‡ c = 11.1–13.8 kcal mol –1 ), which is accompanied by the formation of an intermediate possessing C i symmetry that retains the hydrogen bonds.

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

Probing single-chain conformation and its impact on the optoelectronic properties of donor–accepter conjugated polymers

The chain conformation of donor–acceptor conjugated polymers (D–A CPs) is critical to their optical and electronic properties. However, probing the conformation of D–A CPs (e.g., persistence length and contour length) at a single-chain level is challenging due to the formation of aggregates in dilute solution, even in a good solvent. In this work, we studied the chain conformation and corresponding optical spectra for high-performance D–A CPs in the single-chain state by multimodal variable-temperature scattering and spectroscopy techniques, as well as by molecular dynamics simulations. Here we found a critical role of the side-chain length and branch point in the persistence length and optical absorption due to steric effects. Hence, it is important to consider both the chain rigidity and coplanarity of the polymer backbone to achieve desirable optoelectronic properties. Our findings bridge the fundamental knowledge gaps to design new CPs with desired optoelectronic properties via molecular engineering for next-generation electronic devices.

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

Emerging investigator series: kinetics of diopside reactivity for carbon mineralization in mafic–ultramafic rocks

The ongoing use of fossil fuels to supply modern energy demands has necessitated research on combating carbon dioxide (CO 2 ) emissions and climate change. Carbon storage via mineral trapping in basalt and related rocks is a promising strategy. However, mineralization rates depend on the variable minerology that makes up these rock formations. Diopside (CaMgSi 2 O 6 ) is a common pyroxene mineral in ultramafic and mafic rocks including basalt, but relatively little work has been done to understand its carbon mineralization kinetics using hydrated supercritical CO 2 , which induces the formation of reactive nanoscale interfacial water films. Here, in situ XRD experiments at 50–110 °C and 90 bar indicate that diopside transforms into a myriad of Mg/Ca carbonates, including huntite [Mg 3 Ca(CO 3 ) 4 ] and very high magnesium calcite (VHMC, i.e., protodolomite). Through ex situ characterization, we were able to constrain reaction pathways for the dissolution–precipitation transformation process including metastable intermediate precipitates. Experiments performed at variable temperatures enabled Avrami-derived rate constants and an apparent activation energy of 97 ± 16 kJ mol –1 , implying the dissolution of diopside is the rate-limiting step. Density functional theory (DFT) calculations, used to gain molecular insight into the surface stability of the diopside during dissolution, suggest that exposed calcium cations are susceptible to dissolution when put in contact with water given their coordination environment. The collective results point to the high CO 2 mineralization potential of diopside in basalts, which could help guide parameterization of reactive transport models needed to design and permit commercial-scale subsurface carbon storage operations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗