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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Republished: Colossal density-driven resistance response in the negative charge transfer insulator MnS 2

The Mn chalcogenides show a remarkable variation in structural and physical properties with density. In MnS 2 we observe a pronounced difference with the effects of varying hydrostaticity with pressure inducing a structural transition at 300 K. Within the pyrite phase, a colossal electrical resistance drop of 10 8 Ohms is observed by 12 GPa of nonhydrostatic compression at 300 K. DFT simulations reveal the metallization to be unexpectedly driven by previously unoccupied S$^{2-}_2$ σ$^*_{3p}$ antibonding states crossing the Fermi level. This is a seldom seen variant of the charge transfer insulator to metal transition for negative charge transfer insulators which have anions with an unsaturated valence. Finally, by 36 GPa of nonhydrostatic compression, the single presence of the low-spin insulating arsenopyrite (P2 1 /c) phase is confirmed, and the bulk metallicity is broken with the system returning to an insulative electronic state.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Accelerating Quantum Materials Development with Advances in Transmission Electron Microscopy

Quantum materials are driving a technology revolution in sensing, communication, and computing, while simultaneously testing many core theories of the past century. Materials such as topological insulators, complex oxides, superconductors, quantum dots, color center-hosting semiconductors, and other types of strongly correlated materials can exhibit exotic properties such as edge conductivity, multiferroicity, magnetoresistance, superconductivity, single photon emission, and optical-spin locking. These emergent properties arise and depend strongly on the material’s detailed atomic-scale structure, including atomic defects, dopants, and lattice stacking. In this review, we describe how progress in the field of electron microscopy (EM), including in situ and in operando EM, can accelerate advances in quantum materials and quantum excitations. We begin by describing fundamental EM principles and operation modes. We then discuss various EM methods such as (i) EM spectroscopies, including electron energy loss spectroscopy (EELS), cathodoluminescence (CL), and electron energy gain spectroscopy (EEGS); (ii) four-dimensional scanning transmission electron microscopy (4D-STEM); (iii) dynamic and ultrafast EM (UEM); (iv) complementary ultrafast spectroscopies (UED, XFEL); and (v) atomic electron tomography (AET). We describe how these methods could inform structure–function relations in quantum materials down to the picometer scale and femtosecond time resolution, and how they enable precision positioning of atomic defects and high-resolution manipulation of quantum materials. For each method, we also describe existing limitations to solve open quantum mechanical questions, and how they might be addressed to accelerate progress. Among numerous notable results, our review highlights how EM is enabling identification of the 3D structure of quantum defects; measuring reversible and metastable dynamics of quantum excitations; mapping exciton states and single photon emission; measuring nanoscale thermal transport and coupled excitation dynamics; and measuring the internal electric field and charge density distribution of quantum heterointerfaces- all at the quantum materials’ intrinsic atomic and near atomic-length scale. Finally, we conclude by describing open challenges for the future, including achieving stable sample holders for ultralow temperature (below 10K) atomic-scale spatial resolution, stable spectrometers that enable meV energy resolution, and high-resolution, dynamic mapping of magnetic and spin fields. With atomic manipulation and ultrafast characterization enabled by EM, quantum materials will be poised to integrate into many of the sustainable and energy-efficient technologies needed for the 21st century.

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

Electronic Structure and Epitaxy of CdTe Shells on InSb Nanowires

Abstract Indium antimonide (InSb) nanowires are used as building blocks for quantum devices because of their unique properties, that is, strong spin‐orbit interaction and large Landé g‐factor. Integrating InSb nanowires with other materials could potentially unfold novel devices with distinctive functionality. A prominent example is the combination of InSb nanowires with superconductors for the emerging topological particles research. Here, the combination of the II–VI cadmium telluride (CdTe) with the III–V InSb in the form of core–shell (InSb–CdTe) nanowires is investigated and potential applications based on the electronic structure of the InSb–CdTe interface and the epitaxy of CdTe on the InSb nanowires are explored. The electronic structure of the InSb–CdTe interface using density functional theory is determined and a type‐I band alignment is extracted with a small conduction band offset ( ⩽0.3 eV). These results indicate the potential application of these shells for surface passivation or as tunnel barriers in combination with superconductors. In terms of structural quality, it is demonstrated that the lattice‐matched CdTe can be grown epitaxially on the InSb nanowires without interfacial strain or defects. These shells do not introduce disorder to the InSb nanowires as indicated by the comparable field‐effect mobility measured for both uncapped and CdTe‐capped nanowires.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Prediction of Redox Potentials for the Late Actinides Cm to Lr Using Electronic Structure Methods

Our previously developed computational method for calculating the aqueous redox potentials of the early actinides has been extended to the later elements in the actinide series: Cm, Bk, Cf, Es, Fm, Md, No, and Lr in multiple oxidation states. These calculations were performed using density functional theory with small-core pseudopotentials and their associated basis sets. Solvation effects were considered via a supermolecule-continuum approach, with 30 water molecules representing two solvation shells. Both the COSMO and SMD implicit solvation models were utilized. The structural parameters and hydration numbers for Cm(III), Bk(III), Bk(IV), and Cf(III) are in reasonable agreement with the available experimental data. For redox processes involving atomic cations in solution, the B3LYP/COSMO approach predicted redox potentials to within ±0.2 V of experiment for most redox couples, consistent with our prior work. Inclusion of spin-orbit corrections in specific redox pairs, especially those with the later actinides in high oxidation states, yields improved results relative to calculations including only scalar-relativistic corrections. The An +m /An(0) redox potentials were calculated using a Born-Haber cycle incorporating sublimation, ionization, and hydration energies. Due to a lack of experimental data, three sets of ionization energies were used for the Born-Haber cycle. The calculated An(III/0) potentials showed better agreement with experimental data when using the COSMO solvation model and the test set comprising the NIST recommended ionization energies. Furthermore, the Md(II/0) potential was better described with the SMD model, whereas No(II/0) was not well described by all methods. Finally, the computational approach was able to predict redox potentials that for most cases agreed with the current available experimental or estimated data.

Actinides↗
DOE OSTI2025

Manipulating Aromaticity to Redirect Topochemical Polymerization Pathways

Topochemical polymerization (TCP) represents an essential route to create regio- and stereoregular polymers through solid-state transformations. Herein, we present an innovative strategy for controlling topochemical polymerization pathways by tailoring the terminal group aromaticity in the para-azaquinodimethane (AQM) ring system. Substituting phenyl groups with less aromatic furyl units extends significant spin density delocalization across the conjugated core upon thermal activation, inducing significant diradicaloid characters at furyl positions and enabling unconventional reactivities in both solution and solid states. Thermal treatment in toluene yields a unique cyclophane dimer formed via furyl-methine C-C coupling, confirmed by X-ray crystallography, while solid-state reactions produce polymers formed via both intercolumnar furyl-methine coupling and intracolumnar methine-methine coupling. The spin-center-directed mechanism underlying these transformations is validated through theoretical modeling and isotopic labeling experiments. This study highlights the prowess of aromaticity modulation in functional pro-aromatic systems, which enables the synthesis of polymers with main chain structures that are otherwise difficult to access.

Zhang, Qingsong↗
DOE OSTI2026

Rapidity-dependent spin decomposition of the nucleon

We revisit the two-dimensional Fourier transform of generalized parton distributions (GPDs) at nonzero skewness. At 𝜂 = 0 it reduces to the standard impact-parameter density, while at 𝜂 ≠ 0 it is an off-forward amplitude that we interpret as a genuine parton–nucleon correlation. Its overall strength (the transverse-plane integral of the density) is fixed by the GPD at the kinematic point 𝑡 =−𝑐 𝜂 =−4⁢𝜂 2 ⁢𝑚$^{2}_{𝑁}$/(1 − 𝜂 2 ) and decreases monotonically with the rapidity gap Δ⁢𝑦 = ln⁡[(1+𝜂)/(1−𝜂)] = 2 artanh⁡(𝜂). This rapidity dependence implies rapidity-modified Ji identities that connect helicity, orbital, and total angular momenta of the correlation in closed form. To quantify these effects, we construct leading-twist quark and gluon GPDs in a string-based conformal framework: conformal moments are parametrized by linear open- and closed-string Regge trajectories with slopes constrained by parton distribution functions (PDFs), hadron/glueball spectroscopy, and form-factor data, and GPDs are reconstructed over the full (𝑥,𝜂,𝑡) domain by Mellin-Barnes inversion with next-to-leading order evolution. We find qualitative agreement (and fair quantitative agreement within quoted uncertainties) for several moments and selected nonsinglet 𝑥-space channels at 𝜇 = 2 GeV when compared with lattice QCD, while we also identify channels with visible tension and discuss likely sources (PDF priors and 𝑡-slope systematics).

Gauge-gravity dualities↗
NASA NTRS2014

Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4]

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

electrolytes↗
DOE OSTI2024

Electronic structure, magnetic correlations, and superconducting pairing in the reduced Ruddlesden-Popper bilayer La 3 Ni 2 O 6 under pressure: Different role of d 3 z 2 - r 2 orbital compared with La 3 Ni 2 O 7

The recent discovery of superconductivity in bilayer La 3 Ni 2 O 7 (327-LNO) under pressure stimulated much interest in layered nickelates. However, superconductivity was not found in another bilayer nickelate system, La 3 Ni 2 O 6 (326-LNO), even under pressure. To understand the similarities and differences between 326-LNO and 327-LNO, using density functional theory and the random phase approximation (RPA), we systematically investigate 326-LNO under pressure. The large crystal-field splitting between the e g orbitals caused by the missing apical oxygen moves the d 3z 2 -r 2 orbital farther away from the Fermi level, implying that the d 3z 2 -r 2 orbital plays a less important role in 326-LNO than in 327-LNO. This also results in a smaller bandwidth for the d x 2 -y 2 orbital and a reduced energy gap for the bonding-antibonding splitting of the d 3z 2 -r 2 orbital in 326-LNO, as compared to 327-LNO. Moreover, the in-plane hybridization between the d x 2 -y 2 and d 3z 2 -r 2 orbitals is found to be small in 326-LNO, while it is much stronger in 327-LNO. Furthermore, the low-spin ferromagnetic state is found to be the likely ground state in 326-LNO under high pressure. The weak interlayer coupling suggests that s ± -wave pairing is unlikely in 326-LNO. The robust in-plane ferromagnetic coupling also suggests that d-wave superconductivity, which is usually caused by antiferromagnetic fluctuations of the d x 2 -y 2 orbital, is also unlikely in 326-LNO. These conclusions are supported by our many-body RPA calculations of the pairing behavior. Additionally, contrasting with the cuprates, for the bilayer cuprate HgBa 2 CaCu 2 O 6 , we find a strong self-doping effect of the d x 2 -y 2 orbital under pressure, with the charge of Cu being reduced by approximately 0.13 electrons from 0 GPa to 25 GPa. In contrast, we do not observe such a change in the electronic density in 326-LNO under pressure, establishing another important difference between the nickelates and the cuprates.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Density Functional Theory Study of Controllable Optical Absorptions and Magneto-Optical Properties of Magnetic CrI 3 Nanoribbons: Implications for Compact 2D Magnetic Devices

A chromium triiodide (CrI 3 ) monolayer has an interesting ferromagnetic ground-state. In this work, we calculate band structures and magnetic moments of tensile-strained and bent zigzag CrI 3 nanoribbons with density functional theory. The edge iodine atoms form flat low-lying conduction bands and couple with chromium atoms ferromagnetically, while the non-edge iodine atoms weakly couple antiferromagnetically. Narrow CrI 3 nanoribbons have two locally stable magnetic moment orientations, namely out-of-plane and in-plane (along the nanoribbon periodic direction) configurations. This enables four magnetization states in CrI 3 nanoribbons, including two out-of-plane ones (up and down) and two in-plane ones (forward and backward along the nanoribbon periodical direction), increasing the operating controllability. Based on the one-dimensional Ising spin chain model, the spin correlation length of the narrow CrI 3 nanoribbon is estimated as about 10 Å at its estimated Curie temperature of 27 Kelvin, which is lower than the measured 45 Kelvin of the monolayer CrI 3 . The optical absorption and magneto-optical properties of CrI 3 nanoribbons are investigated with many-body perturbation GW-BSE (Bethe-Salpeter equation), including magnetic dichroism, Faraday and magneto-optical Kerr effects. Here, the low-energy dark excitons are mainly from transitions between electrons and holes with unlike spins and are non-Frenkel-like, while the bright excitons have mixed spin configurations. The intrinsic lifetime of excitons can be over one nanosecond, suitable for quantum information processes. Tensile strains and bending manifestly modulate the absorption spectra and magneto-optical properties of CrI 3 nanoribbons within a technologically important photon energy-range of ~1.0-2.0 eV. The CrI 3 nanoribbons can be used in 1D or 2D magnetic storage nanodevices, tunable magnetic optoelectronics, and spin-based quantum information controls.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ab initio typical medium theory of substitutional disorder

Here, by merging single-site typical medium theory with density-functional theory, we introduce a self-consistent framework for electronic-structure calculations of materials with substitutional disorder which takes into account Anderson localization. The scheme and details of the implementation are presented and applied to the hypothetical alloy Li$_cBe_{1-c}$, and the results are compared with those obtained with the coherent potential approximation. Furthermore, we demonstrate that Anderson localization suppresses ferromagnetic order for a very low concentration of (i) carbon impurities substituting oxygen in $MgO_{1-c}C_c$ and (ii) manganese impurities substituting magnesium in $Mg_{1-c}Mn_cO$ for the low-spin magnetic configuration.

36 MATERIALS SCIENCE↗
NASA NTRS1984

Magnetically suspended flywheel system study

A program to study the application of a graphite/epoxy, magnetically suspended, pierced disk flywheel for the combined function of spacecraft attitude control and energy storage (ACES) is described. Past achievements of the program include design and analysis computer codes for the flywheel rotor, a magnetically suspended flywheel model, and graphite/epoxy rotor rings that were successfully prestressed via interference assembly. All hardware successfully demonstrated operation of the necessary subsystems which form a complete ACES design. Areas of future work include additional rotor design research, system definition and control strategies, prototype development, and design/construction of a UM/GSFC spin test facility. The results of applying design and analysis computer codes to a magnetically suspended interference assembled rotor show specific energy densities of 42 Wh/lb (92.4 Wh/kg) are obtained for a 1.6 kWh system.

Kirk, J. A.↗
DOE OSTI2021

Effects of Site and Magnetic Disorder on the Oxygen Vacancy Formation and Electronic and Optical Properties of La x Sr 1– x CoO 3–δ and SrFe y Co 1– y O 3–δ [plus supplemental information]

Disorder is an inevitable issue in practical applications of perovskites with the A-site occupied by La/Sr and the B-site occupied by Co/Fe. We performed density functional theory calculations to reveal the site and magnetic disorder effect on the oxygen vacancy formation and the electronic and optical properties of La x Sr 1–x CoO 3–δ and SrFe y Co 1–y O 3–δ systems. Generally, site disorder has little influence on the physical properties we studied, while magnetic disorder has a property-dependent effect for La A-site and Fe B-site doping of SrCoO 3 . Compared to ordered ferromagnetic (FM) calculations, disordered paramagnetic (PM) results can better describe the high-temperature behavior of lattice expansion and the multiple spin states of Co ions in La x Sr 1–x CoO 3 . The oxygen vacancy formation energy results show that the magnetic disorder has a more remarkable effect on SrFe y Co 1–y O 3–δ systems with a robust magnetic order than that on the La x Sr 1–x CoO 3–δ systems with a fragile magnetic order. The electronic structures in the PM phase have less spin polarization and broadened bands, by which the optical absorptions from the single spin channel transition in the FM phase have an obvious change in the magnitude and/or the trend. Furthermore, our work provides guidance for where and why to consider the disorder.

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

From Trivial Kondo Insulator Ce 3 Pt 3 Bi 4 to Topological Nodal-Line Semimetal Ce 3 Pd 3 Bi 4

In this work, using the density functional theory combined with dynamical mean-field theory, we have performed systematic study of the electronic structure and its band topology properties of Ce 3 Pt 3 Bi 4 and Ce 3 Pd 3 Bi 4 . At high temperatures ( ~ 290 K ), the electronic structures of both compounds resemble the open-core 4 f density functional calculation results. For Ce 3 Pt 3 Bi 4 , clear hybridization gap can be observed below 72 K, and its coherent momentum-resolved spectral function below 18 K exhibits an topologically trivial indirect gap of ~ 6 meV and resembles density functional band structure with itinerant 4 f state. For Ce 3 Pd 3 Bi 4 , no clear hybridization gap can be observed down to 4 K, and its momentum-resolved spectral function resembles electron-doped open-core 4 f density functional calculations. The band nodal points of Ce 3 Pd 3 Bi 4 at 4 K are protected by the gliding-mirror symmetry and form ringlike structure. Therefore, the Ce 3 Pt 3 Bi 4 compound is topologically trivial Kondo insulator while the Ce 3 Pd 3 Bi 4 compound is topological nodal-line semimetal.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Recent Progress on Topological Structures in Ferroic Thin Films and Heterostructures

Topological spin/polarization structures in ferroic materials continue to draw great attention as a result of their fascinating physical behaviors and promising applications in the field of high-density nonvolatile memories as well as future energy-efficient nanoelectronic and spintronic devices. Such developments have been made, in part, based on recent advances in theoretical calculations, the synthesis of high-quality thin films, and the characterization of their emergent phenomena and exotic phases. Herein, progress over the last decade in the study of topological structures in ferroic thin films and heterostructures is explored, including the observation of topological structures and control of their structures and emergent physical phenomena through epitaxial strain, layer thickness, electric, magnetic fields, etc. First, the evolution of topological spin structures (e.g., magnetic skyrmions) and associated functionalities (e.g., topological Hall effect) in magnetic thin films and heterostructures is discussed. Then, the exotic polar topologies (e.g., domain walls, closure domains, polar vortices, bubble domains, and polar skyrmions) and their emergent physical properties in ferroelectric oxide films and heterostructures are explored. Lastly, a brief overview and prospectus of how the field may evolve in the coming years is provided.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tunable band gaps and optical absorption properties of bent MoS2 nanoribbons

Abstract The large tunability of band gaps and optical absorptions of armchair MoS 2 nanoribbons of different widths under bending is studied using density functional theory and many-body perturbation GW and Bethe–Salpeter equation approaches. We find that there are three critical bending curvatures, and the non-edge and edge band gaps generally show a non-monotonic trend with bending. The non-degenerate edge gap splits show an oscillating feature with ribbon width n , with a period $$\Delta n=3$$ Δ n = 3 , due to quantum confinement effects. The complex strain patterns on the bent nanoribbons control the varying features of band structures and band gaps that result in varying exciton formations and optical properties. The binding energy and the spin singlet–triplet split of the exciton forming the lowest absorption peak generally decrease with bending curvatures. The large tunability of optical properties of bent MoS 2 nanoribbons is promising and will find applications in tunable optoelectronic nanodevices.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Symmetries and spectral statistics in chaotic conformal field theories

We discuss spectral correlations in coarse-grained chaotic two-dimensional CFTs with large central charge. We study a partition function describing the dense part of the spectrum of primary states in a way that disentangles the chaotic properties of the spectrum from those which are a consequence of Virasoro symmetry and modular invariance. We argue that random matrix universality in the near-extremal limit is an independent feature of each spin sector separately; this is a non-trivial statement because the exact spectrum is fully determined by only the spectrum of spin zero primaries and those of a single non-zero spin (“spectral determinacy”). We then describe an argument analogous to the one leading to Cardy’s formula for the averaged density of states, but in our case applying it to spectral correlations: assuming statistical universalities in the near-extremal spectrum in all spin sectors, we find similar random matrix universality in a large spin regime far from extremality.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Hund's metal physics: From SrNiO 2 to LaNiO 2

We study the normal state electronic structure of the recently discovered infinite-layer nickelate superconductor, Nd 1-x Sr x NiO 2 , using density functional theory plus dynamical mean-field theory calculations. Starting with the multiorbital compound SrNiO 2 , our calculations show that despite large charge-carrier doping from SrNiO 2 to LaNiO 2 , the Ni-3d total occupancy is barely changed due to the decreased hybridization with the occupied oxygen-2p states and increased hybridization with the unoccupied La-5d states. Thus, using SrNiO 2 as a reference, La 1-x Sr x NiO 2 is naturally and conclusively found to be a multiorbital electronic system with characteristic Hund's metal behaviors, such as metallicity, the importance of high-spin configurations, tendency towards orbital differentiation, and the absence of magnetism in regimes which are ordered according to static mean-field theories. Finally, our results are in good agreement with the existing spectroscopic studies and make an essential step towards an understanding of the electronic structures of Nd 1-x Sr x NiO 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗