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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 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Edge States Drive Exciton Dissociation in Ruddlesden–Popper Lead Halide Perovskite Thin Films

Efficient photovoltaic cells based on thin films of solution-processed 2D Ruddlesden–Popper hybrid perovskites (RPPs) represent an exciting breakthrough due to their enhanced tunability and chemical stability relative to those fabricated from 3D phases. However, reports of efficient charge separation and current collection are in apparent contradiction with the well-known enhancement of the exciton binding energy in multilayered halide perovskites, which should lower the device’s internal quantum efficiency and voltage. This controversy has led to various proposals for the electronic and physical structure of RPP thin films, including phase inhomogeneity as the driving force for exciton dissociation and transport. We address this apparent paradox in high-quality hot-cast RPP films by correlating ultrafast transient absorption spectroscopy with X-ray scattering measurements. We show that a hot-casting fabrication method produces highly phase pure n = 3 (BA) 2 (MA) n-1 Pb n I 3n+1 RPP structures. The high-phase purity and large grain sizes allow us to observe vertical transport of excitons via a diffusive process and allow us to determine that charge separation is primarily driven by dissociation at surface localized subgap electronic states. Furthermore, we analyze the differential absorption kinetics in films of varying thickness to directly determine that the excitonic diffusion constant is ~0.18 cm 2 s –1 . We propose that a surface localized structural distortion, observed using surface selective grazing incidence X-ray scattering measurements, is responsible for the creation of the surface localized defect states. We find that the density and spatial distribution of these defect states is a function of preparation conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Machine learning without a processor: Emergent learning in a nonlinear analog network

Standard deep learning algorithms require differentiating large nonlinear networks, a process that is slow and power-hungry. Electronic contrastive local learning networks (CLLNs) offer potentially fast, efficient, and fault-tolerant hardware for analog machine learning, but existing implementations are linear, severely limiting their capabilities. These systems differ significantly from artificial neural networks as well as the brain, so the feasibility and utility of incorporating nonlinear elements have not been explored. Here, we introduce a nonlinear CLLN—an analog electronic network made of self-adjusting nonlinear resistive elements based on transistors. We demonstrate that the system learns tasks unachievable in linear systems, including XOR (exclusive or) and nonlinear regression, without a computer. We find our decentralized system reduces modes of training error in order (mean, slope, curvature), similar to spectral bias in artificial neural networks. The circuitry is robust to damage, retrainable in seconds, and performs learned tasks in microseconds while dissipating only picojoules of energy across each transistor. This suggests enormous potential for fast, low-power computing in edge systems like sensors, robotic controllers, and medical devices, as well as manufacturability at scale for performing and studying emergent learning.

Science & Technology - Other Topics↗
DOE OSTI2022

Sachdev-Ye-Kitaev models and beyond: Window into non-Fermi liquids

In this work is a review of the Sachdev-Ye-Kitaev (SYK) model of compressible quantum many-body systems without quasiparticle excitations, and its connections to various theoretical studies of non-Fermi liquids in condensed matter physics. The review is placed in the context of numerous experimental observations on correlated electron materials. Strong correlations in metals are often associated with their proximity to a Mott transition to an insulator created by the local Coulomb repulsion between the electrons. The phase diagrams of a number of models of such a local electronic correlation are explored, employing a dynamical mean-field theory in the presence of random spin exchange interactions. Numerical analyses and analytical solutions, using renormalization group methods and expansions in large spin degeneracy, lead to critical regions that display SYK physics. The models studied include the single-band Hubbard model, the t–J model, and the two-band Kondo-Heisenberg model in the presence of random spin exchange interactions. Also examined are non-Fermi liquids obtained by considering each SYK model with random four-fermion interactions to be a multiorbital atom, with the SYK atoms arranged in an infinite lattice. Connections are made to theories of sharp Fermi surfaces without any low-energy quasiparticles in the absence of spatial disorder, obtained by coupling a Fermi liquid to a gapless boson; a systematic large-N theory of such a critical Fermi surface, with SYK characteristics, is obtained by averaging over an ensemble of theories with random boson-fermion couplings. Finally, an overview of the links between the SYK model and quantum gravity is presented, and the review ends with an outlook on open questions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Interplay between Local Moment and Itinerant Magnetism in the Layered Metallic Antiferromagnet TaFe 1.14 Te 3

Two-dimensional antiferromagnets have garnered considerable interest for the next generation of functional spintronics. However, many bulk materials from which two-dimensional antiferromagnets are isolated are limited by their air sensitivity, low ordering temperatures, and insulating transport properties. TaFe 1+y Te 3 aims to address these challenges with increased air stability, metallic transport, and robust antiferromagnetism. Here, we synthesize TaFe 1+y Te 3 (y = 0.14), identify its structural, magnetic, and electronic properties, and elucidate the relationships between them. Axial-dependent high-field magnetization measurements on TaFe 1.14 Te 3 reveal saturation magnetic fields ranging between 27-30 T with saturation magnetic moments of 2.05- 2.12 μ B . Magnetotransport measurements confirm TaFe 1.14 Te 3 is metallic with strong coupling between magnetic order and electronic transport. Angle-resolved photoemission spectroscopy measurements across the magnetic transition uncover a complex interplay between itinerant electrons and local magnetic moments that drives the magnetic transition. In conclusion, we demonstrate the ability to isolate few-layer sheets of TaFe 1.14 Te 3 , establishing TaFe 1.14 Te 3 as a potential platform for two-dimensional spintronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Site-specific electronic structure of covalently linked bimetallic dyads from nitrogen K-edge x-ray absorption spectroscopy

A nitrogen K-edge x-ray absorption near-edge structure (XANES) survey is presented for tetrapyrido[3,2-a:',3'-c:3'',2''-h:2''',3'''-j]phenazine (tpphz)-bridged bimetallic assemblies that couple chromophore and catalyst transition metal complexes for light driven catalysis, as well as their individual molecular constituents. We demonstrate the high N site sensitivity of the N pre-edge XANES features, which are energetically well-separated for the phenazine bridge N atoms and for the individual metal-bound N atoms of the inner coordination sphere ligands. By comparison with the time-dependent density functional theory calculated spectra, we determine the origins of these distinguishable spectral features. We find that metal coordination generates large shifts toward higher energy for the metal-bound N atoms, with increasing shift for 3d < 4d < 5d metal bonding. This is attributed to increasing ligand-to-metal σ donation that increases the effective charge of the bound N atoms and stabilizes the N 1s core electrons. In contrast, the phenazine bridge N pre-edge peak is found at a lower energy due to stabilization of the low energy electron accepting orbital localized on the phenazine motif. While no sensitivity to ground state electronic coupling between the individual molecular subunits was observed, the spectra are sensitive to structural distortions of the tpphz bridge. Here these results demonstrate N K-edge XANES as a local probe of electronic structure in large bridging ligand motifs, able to distinctly investigate the ligand-centered orbitals involved in metal-to-ligand and ligand-to-ligand electron transfer following light absorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1989

Parallel electric fields in a simulation of magnetotail reconnection and plasmoid evolution

Properties of the electric field component parallel to the magnetic field (E sub parallel) in a three-dimensional MHD simulation of plasmoid formation and evolution in the magnetotail in the presence of a net dawn-dusk magnetic field component were observed. Particularly emphasized was the spatial location of E(sub parallel), the concept of a diffusion zone and the role of E(sub parallel) in accelerating electrons. A localization of the region of enhanced E(sub parallel) in all space directions with a strong concentration in the z direction was found. This region was identified as the diffusion zone, which plays a crucial role in reconnection theory through the local break-down of magnetic flux conservation. The presence of B(sub y) implies a north-south asymmetry of the injection of accelerated particles into the near-earth region, if the net B(sub y) field is strong enough to force particles to follow field lines through the diffusion region. It is estimated that for a typical net B(sub y) field this should affect the injection of electrons into the near-earth dawn region, so that precipitation into the Northern (Southern) Hemisphere should dominate for duskward (dawnward) net B(sub y). In addition, a spatial clottiness of the expected injection of adiabatic particles which could be related to the appearance bright spots in auroras was observed.

Hesse, Michael↗
DOE OSTI2021

Navigating Transition-Metal Chemical Space: Artificial Intelligence for First-Principles Design

Conspectus The variability of chemical bonding in open-shell transition-metal complexes not only motivates their study as functional materials and catalysts but also challenges conventional computational modeling tools. Here, tailoring ligand chemistry can alter preferred spin or oxidation states as well as electronic structure properties and reactivity, creating vast regions of chemical space to explore when designing new materials atom by atom. Although first-principles density functional theory (DFT) remains the workhorse of computational chemistry in mechanism deduction and property prediction, it is of limited use here. DFT is both far too computationally costly for widespread exploration of transition-metal chemical space and also prone to inaccuracies that limit its predictive performance for localized d electrons in transition-metal complexes. These challenges starkly contrast with the well-trodden regions of small-organic-molecule chemical space, where the analytical forms of molecular mechanics force fields and semiempirical theories have for decades accelerated the discovery of new molecules, accurate DFT functional performance has been demonstrated, and gold-standard methods from correlated wavefunction theory can predict experimental results to chemical accuracy. The combined promise of transition-metal chemical space exploration and lack of established tools has mandated a distinct approach. In this Account, we outline the path we charted in exploration of transition-metal chemical space starting from the first machine learning (ML) models (i.e., artificial neural network and kernel ridge regression) and representations for the prediction of open-shell transition-metal complex properties. The distinct importance of the immediate coordination environment of the metal center as well as the lack of low-level methods to accurately predict structural properties in this coordination environment first motivated and then benefited from these ML models and representations. Once developed, the recipe for prediction of geometric, spin state, and redox potential properties was straightforwardly extended to a diverse range of other properties, including in catalysis, computational “feasibility”, and the gas separation properties of periodic metal–organic frameworks. Interpretation of selected features most important for model prediction revealed new ways to encapsulate design rules and confirmed that models were robustly mapping essential structure–property relationships. Encountering the special challenge of ensuring that good model performance could generalize to new discovery targets motivated investigation of how to best carry out model uncertainty quantification. Distance-based approaches, whether in model latent space or in carefully engineered feature space, provided intuitive measures of the domain of applicability. With all of these pieces together, ML can be harnessed as an engine to tackle the large-scale exploration of transition-metal chemical space needed to satisfy multiple objectives using efficient global optimization methods. In practical terms, bringing these artificial intelligence tools to bear on the problems of transition-metal chemical space exploration has resulted in ML-model assessments of large, multimillion compound spaces in minutes and validated new design leads in weeks instead of decades.

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

Unusual Role of Point Defects in Perovskite Nickelate Electrocatalysts

Low-cost transition-metal oxide is regarded as a promising electrocatalyst family for an oxygen evolution reaction (OER). The classic design principle for an oxide electrocatalyst believes that point defect engineering, such as oxygen vacancies (VO .. ) or heteroatom doping, offers the opportunities to manipulate the electronic structure of material toward optimal OER activity. Oppositely, in this work, we discover a counterintuitive phenomenon that both VO .. and an aliovalent dopant (i.e., proton (H + )) in perovskite nickelate (i.e., NdNiO 3 (NNO)) have a considerably detrimental effect on intrinsic OER performance. Detailed characterizations unveil that the introduction of these point defects leads to a decrease in the oxidative state of Ni and weakens Ni-O orbital hybridization, which triggers the local electron-electron correlation and a more insulating state. Evidenced by first-principles calculation using the density functional theory (DFT) method, the OER on nickelate electrocatalysts follows the lattice oxygen mechanism (LOM). The incorporation of point defect increases the energy barrier of transformation from OO*(V O ) to OH*(V O ) intermediates, which is regarded as the rate-determining step (RDS). Furthermore, this work offers a new and significant perspective of the role that lattice defects play in the OER process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Voyager planetary radio astronomy studies

Analysis of nonthermal radio emission data obtained by the Planetary Radio Astronomy (PRA) spectrometers on the Voyager 1 and 2 spacecraft was performed. This PRA data provided unique insights into the radio emission characteristics of the outer planets because of PRA's unique spectral response below the terrestrial ionospheric plasma frequency and its unprecedented proximity to the source. Of those results which were documented or published, this final report surveys only the highlights and cites references for more complete discussions. Unpublished results for Uranus, Neptune, and theoretical Ionian current distributions are presented at greater length. The most important conclusion to be drawn from these observations is that banded spectral emission is common to the radio emission below 1-2 MHz observed from all four Jovian planets. In every case multiple spectral features evolve on time scales of seconds to minutes. To the extent these features drift in frequency, they appear never to cross one another. The Neptunian spectral features appear to drift little or not at all, their evolution consisting principally of waxing and waning. Since other evidence strongly suggests that most or all of this radio emission is occurring near the local magnetospheric electron cyclotron frequency, this implies that this emission preferentially occurs at certain continually changing planetary radii. It remains unknown why certain radii might be favored, unless radial electric field components or other means serve to differentiate radially the magnetospheric plasma density, particle energy vectors, or particle coherence. Calculation of the spatial distribution and intensity of the Io-generated magnetospheric currents are also presented; these currents may be limited principally by wave impedance and local field strengths.

Staelin, David H.↗
DOE OSTI2021

Deterministic scattering of relativistic electron beams by off-resonant circularly polarized electromagnetic waves

A mechanism is presented whereby relativistic electron beams localized in phase space are deterministically scattered by coherent circularly polarized electromagnetic waves without stochastic processes. It is shown via an exact single-particle analysis that the condition for maximal scattering is an off-resonant condition, contrary to previous kinetic analyses that predict maximal diffusion or interaction at exact resonance or its harmonics. The mechanism, verified by single-particle simulations, enables a fast, nonlinear redistribution of the beam particles. A possible application of this mechanism to runaway electron suppression is presented.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Towards isolated attosecond electron bunches using ultrashort-pulse laser-solid interactions

We investigate MeV-level attosecond electron bunches from ultrashort-pulse laser-solid interactions through similarities between experimental and simulated electron energy spectra. We show measurements of the bunch duration and temporal structure from particle-in-cell simulations. The experimental observation of such bunches favors specular reflection direction when focusing the laser pulse onto a subwavelength boundary of thick overdense plasmas at grazing incidence. Particle-in-cell simulation further reveals that the attosecond duration is a result of ultra-thin (~tenth of a micron) gaps of zero electromagnetic energy density in the modulated reflected radiation, while the bunching (locally peaked electron concentration) comes from the highly-directional electron angular distribution acquired by the electrons in a grazing incidence setup. To isolate a single electron bunch, we perform simulations using 1-cycle laser pulses and analyze the effect of carrier-envelop phase with particle tracking. The duration of the electron bunch can be further decreased by increasing the laser intensity and the focal spot size, while its direction can be changed by tuning the preplasma density gradient.

High-harmonic generation↗
DOE OSTI2022

Pressure-induced concomitant topological and metal-insulator quantum phase transitions in Ce3Pd3Bi4

Abstract The electronic property and magnetic susceptibility of Ce 3 Pd 3 Bi 4 were systemically investigated from 18 to 290 K for varying values of cell volume using dynamic mean-field theory coupled with density functional theory. By extrapolating to zero temperature, the ground state of Ce 3 Pd 3 Bi 4 at ambient pressure is found to be a correlated semimetal due to insufficient hybridization. Upon applying pressure, the hybridization strength increases and a crossover to the Kondo insulator is observed at finite temperatures. The characteristic temperature signaling the formation of Kondo singlet, as well as the characteristic temperature associated with f -electron delocalization–localization change, simultaneously vanishes around a critical volume of 0.992 V 0 , suggesting that such metal–insulator transition is possibly associated with a quantum critical point. Finally, Wilson’s loop calculations indicate that the Kondo insulating side is topologically trivial, thus a topological transition also occurs across the quantum critical point.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Facile ab initio approach for self-localized polarons from canonical transformations

Electronic states in a crystal can localize due to strong electron-phonon (e-ph) interactions, forming so-called small polarons. Methods to predict the formation and energetics of small polarons are either computationally costly or not geared toward quantitative predictions. Here we show a formalism based on canonical transformations to compute the polaron formation energy and wave function using ab initio e-ph interactions. Comparison of the calculated polaron and band-edge energies allows us to determine whether charge carriers in a material favor a localized small polaron over a delocalized Bloch state. Due to its low computational cost, our approach enables efficient studies of the formation and energetics of small polarons, as we demonstrate by investigating electron and hole polaron formation in alkali halides and metal oxides and peroxides. We outline refinements of our scheme and extensions to compute transport in the polaron hopping regime.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Pathways for Electron Transfer at MgO–Water Interfaces from Ab Initio Molecular Dynamics

The nature of electron transfer across metal oxide–water interfaces depends significantly on the band gap of the oxide and its band edge energies relative to the potentials of relevant aqueous redox couples. Here we focus on the water interface with MgO, a prototypical wide band gap oxide whose conduction band edge is close in energy to that of water. We investigate the behavior of an excess electron at and out of equilibrium near the interface using ab initio molecular dynamics based on hybrid density functional theory. Our simulations show that under equilibrium conditions the excess electron (donated by an Al impurity in MgO) localizes to a midgap defect state comparable in energy and shape to a hydrated electron in bulk water. To characterize the electron transfer from the conduction band of MgO to interfacial product states, we dope near-equilibrium configurations of the pristine MgO–water system with Al and run short trajectories of these instantaneously out-of-equilibrium systems. Here we observe two distinct products associated with the excess electron: a surface-localized electron (e surf –) and an aqueous hydrogen radical (H • ). The H • pathway exhibits a much higher activation barrier despite being more exoergic, making e surf – the kinetic product. Our characterization of the pathways on the basis of Marcus theory is consistent with the poor observed utility of MgO for water radiolysis. Moreover, we anticipate that the computational framework employed here will be broadly applicable to assessing electron transfer mechanisms at aqueous, photocatalytic interfaces.

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

Morphology Effects on Free Energies of Proton-Coupled Electron Transfer in Polyoxotungstates

Polyoxotungstates have previously been established to facilitate the hydrogenation of small molecule substrates via hydrogen atom transfer from reactive hydroxyl groups formed at the assembly surface. Understanding structure−function relationships that dictate the thermochemistry and kinetics of protoncoupled electron transfer is key to controlling this chemistry. In this work, we combine comprehensive electrochemical experiments and density functional theory calculations to address how different polyoxotungstate morphologies, specifically W 6 O 19 −2 , W 10 O 32 −4 , SiW 12 O 40 −4 , and P 2 W 18 O 62 −6 , affect the bond dissociation free energies of surface hydroxides (BDFE(O−H)) formed upon reduction of the assembly in acidic media. Our results reveal increasing hydroxide bond strengths with increasing cluster size, and that anisotropic cluster geometries result in substantial thermodynamic differentiation of H-binding sites. We demonstrate an excellent agreement between theory and experiments on the reported BDFE(O−H) values and, importantly, we elucidate how cluster size and shape affect electronic properties (local charges and frontier molecular orbitals), giving rise to sites with increased preference for hydrogen binding, demonstrated in higher BDFE(O−H). Overall, this work aids the understanding and design of polyoxometalates exhibiting surface sites with tailored interaction strengths.

anions↗
DOE OSTI2022

Unified Approach to Polarons and Phonon-Induced Band Structure Renormalization

Ab initio calculations of the phonon-induced band structure renormalization are currently based on the perturbative Allen-Heine theory and its many-body generalizations. These approaches are unsuitable to describe materials where electrons form localized polarons. Here, we develop a self-consistent, many-body Green’s function theory of band structure renormalization that incorporates localization and self-trapping. Here, we show that the present approach reduces to the Allen-Heine theory in the weak-coupling limit, and to total energy calculations of self-trapped polarons in the strong-coupling limit. To demonstrate this methodology, we reproduce the path-integral results of Feynman and diagrammatic Monte Carlo calculations for the Fröhlich model at all couplings, and we calculate the zero point renormalization of the band gap of an ionic insulator including polaronic effects.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗