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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Spin dynamics of [1,2- 13 C 2 ]pyruvate hyperpolarization by parahydrogen in reversible exchange at micro Tesla fields

Hyperpolarization of 13 C-pyruvate via Signal Amplification By Reversible Exchange (SABRE) is an important recent discovery because of both the relative simplicity of hyperpolarization and the central biological relevance of pyruvate as a biomolecular probe for in vitro or in vivo studies. Here, we analyze the [1,2- 13 C 2 ]pyruvate-SABRE spin system and its field dependence theoretically and experimentally. We provide first-principles analysis of the governing 4-spin dihydride- 13 C 2 Hamiltonian and numerical spin dynamics simulations of the 7-spin dihydride- 13 C 2 –CH 3 system. Furthermore, the analytical and the numerical results are compared to matching systematic experiments. With these methods we unravel the observed spin state mixing of singlet states and triplet states at microTesla fields and we also analyze the dynamics during transfer from micro-Tesla field to high field for detection to understand the resulting spectra from the [1,2- 13 C 2 ]pyruvate-SABRE system.

13C pyruvate↗
DOE OSTI2023

Impact of Chiral Symmetry Breaking on Spin-Texture and Lone Pair Expression in Chiral Crystals of Hybrid Antimony and Bismuth Halides

Chiral organic building blocks can be incorporated into hybrid organic-inorganic metal-halide crystalline semiconductors so as to control and impact the interconversion between light, charge, and spin. Here, we report a series of hybrid antimony and bismuth halide materials of the general formula MBA 4 B 2 X 10 (B = Sb 3+ , Bi 3+ ; X = Br - , I - ) and study how chiral symmetry breaking imposed by the templating organic chiral methylbenzylammonium (MBA) cations induces symmetry breaking within the inorganic sublattice and leads to a unique spin-texture. The chiral MBA cations introduce two structural modifications to the metal-halide sublattice that consists of isolated edge-sharing dimers of B 2 X 10 octahedra: (1) the dimers have a chiral spatial arrangement with respect to one another and (2) there is an asymmetric distortion of the two subunits within the individual dimers with a higher distortion caused by strong stereochemical activity of the Sb 5s 2 lone pair electrons. The structural distortions and chiral arrangement result in circular dichroism (CD) at the band edge of the inorganic framework with dissymmetry factors in the range of 10 -4 . Chiral spin-splitting of the inorganic states, caused by breaking of the inversion symmetry and large spin-orbit coupling, is studied via density functional theory (DFT), and a multiband effective mass theory was developed that links the DFT-derived spin-splitting of helical character (i.e., spin expectation value not perpendicular to the crystal momentum) to the observed CD. Furthermore, we also find broad red photoluminescence from the MBA 4 Sb 2 Br 10 compounds, which we attribute to self-trapped excitonic emission driven by the large distortion due to the lone pair expression.

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

Computational tools for the simulation and analysis of spin-polarized EPR spectra

The EPR spectra of paramagnetic species induced by photoexcitation typically exhibit enhanced absorptive and emissive features resulting from sublevel populations that differ from thermal equilibrium. The populations and the resulting spin polarization of the spectra are dictated by the selectivity of the photophysical process generating the observed state. Simulation of the spin-polarized EPR spectra is crucial in the characterization of both the dynamics of formation of the photoexcited state as well as its electronic and structural properties. EasySpin, the simulation toolbox for EPR spectroscopy, now includes extended support for the simulation of the EPR spectra of spin-polarized states of arbitrary spin multiplicity and formed by a variety of different mechanisms, including photoexcited triplet states populated by intersystem crossing, charge recombination or spin polarization transfer, spin-correlated radical pairs created by photoinduced electron transfer, triplet pairs formed by singlet fission and multiplet states arising from photoexcitation in systems containing chromophores and stable radicals. In this paper, we highlight EasySpin’s capabilities for the simulation of spin-polarized EPR spectra on the basis of illustrative examples from the literature in a variety of fields ranging across chemistry, biology, material science and quantum information science.

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

Magnetic Imaging with Spin Defects in Hexagonal Boron Nitride

Optically active spin defects hosted in hexagonal boron nitride (ℎ-BN) are promising candidates for the development of a two-dimensional (2D) quantum sensing unit. Here, we demonstrate quantitative magnetic imaging with ℎ-BN flakes doped with negatively charged boron-vacancy ($V^{-}_{B}$) centers through neutron irradiation. As a proof-of-concept, we image the magnetic field produced by Cr⁢Te 2 , a van der Waals ferromagnet with a Curie temperature slightly above 300 K. Compared to other quantum sensors embedded in 3D materials, the advantages of the ℎ-BN-based magnetic sensor described in this work are its ease of use, high flexibility, and, more importantly, its ability to be placed in close proximity to a target sample. Further, such a sensing unit will likely find numerous applications in 2D materials research by offering a simple way to probe the physics of van der Waals heterostructures.

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

Spectral Addressability in a Modular Two Qubit System

The combination of structural precision and reproducibility of synthetic chemistry is perfectly suited for the creation of chemical qubits, the core units of a quantum information science (QIS) system. By exploiting the atomistic control inherent to synthetic chemistry, we address a fundamental question of how the spin–spin distance between two qubits impacts electronic spin coherence. To achieve this goal, in this study we designed a series of molecules featuring two spectrally distinct qubits, an early transition metal, Ti 3+ , and a late transition metal, Cu 2+ with increasing separation between the two metals. The spectral separation between the two metals enables us to probe each metal individually in the bimetallic species and compare it with monometallic control samples. Coherence times found to be governed by the distance to nuclear spins on the other qubit’s ligand framework. This finding offers guidance for the design of spectrally addressable molecular qubits.

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

Topotactic Reduction‐Driven Crystal Field Excitations in Brownmillerite Manganite Thin Films

Topotactic reduction of perovskite oxides offers a powerful approach for discovering novel phenomena, such as superconducting infinite-layer nickelates and polar metallicity, and is commonly accompanied by the emergence of multiple valence states and/or complex crystal fields of transition metals. However, understanding the complex interplay between crystal chemistry, electronic structure, and physical properties at the spin- and orbital-resolved levels in these reduced systems remains elusive. Here, in this study, x-ray absorption spectroscopy, resonant inelastic x-ray scattering (RIXS), and density functional theory calculations are used to uncover topotactic metal-insulator transition and orbital-specific crystal field excitations in brownmillerite La 0.67 Ca 0.33 MnO 2.5 thin films. The Mn valence states are found to be Mn 2+ /Mn 3+ , along with their corresponding populations at octahedral and tetrahedral sites, which effectively weaken the Mn-O hybridization compared to the parent perovskite phase. As a result, La 0.67 Ca 0.33 MnO 2.5 films exhibit an antiferromagnetic insulating ground state. Moreover, by combining the RIXS measurements on selected single-valence manganites, specifically MnO, LaMnO 3 , and CaMnO 3 , with orbital- and spin-resolved density-of-states calculations, the study identifies the dd excitations of octahedrally and tetrahedrally coordinated Mn 2+ /Mn 3+ ions, directly linking the microscopic electronic structure to the macroscopic magnetic/electrical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Effect of Anisotropic Confinement on Electronic Structure and Dynamics of Band Edge Excitons in Inorganic Perovskite Nanowires

Inorganic lead halide perovskite nanostructures show promise as the active layers in photovoltaics, light emitting diodes, and other optoelectronic devices. They are robust in the presence of oxygen and water, and the electronic structure and dynamics of these nanostructures can be tuned through quantum confinement. Here we create aligned bundles of CsPbBr3 nanowires with widths resulting in quantum confinement of the electronic wave functions and subject them to ultrafast microscopy. We directly image rapid one-dimensional exciton diffusion along the nanowires, and we measure an exciton trap density of roughly one per nanowire. Using transient absorption microscopy, we observe a polarization-dependent splitting of the band edge exciton line, and from the polarized fluorescence of nanowires in solution, we determine that the exciton transition dipole moments are anisotropic in strength. Furthermore, our observations are consistent with a model in which splitting is driven by shape anisotropy in conjunction with long-range exchange.

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

Melting of charge order in the low-temperature state of an electronic ferroelectric-like system

Strong electronic interactions can drive a system into a state with a symmetry breaking. Lattice frustration or competing interactions tend to prevent symmetry breaking, leading to quantum disordered phases. In spin systems frustration can produce a spin liquid state. Frustration of a charge degree of freedom also can result in various exotic states, however, experimental data on these effects is scarce. In this work we demonstrate how in a Mott insulator on a weakly anisotropic triangular lattice a charge ordered state melts on cooling down to low temperatures. Raman scattering spectroscopy finds that κ -(BEDT-TTF) 2 Hg(SCN) 2 Cl enters an insulating “dipole solid” state at T =30K, but below T =15K the order melts, while preserving the insulating energy gap. Based on these observations, we suggest a phase diagram relevant to other quantum paraelectric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Iron-based binary ferromagnets for transverse thermoelectric conversion

Thermoelectric generation using the anomalous Nernst effect (ANE) has great potential for application in energy harvesting technology because the transverse geometry of the Nernst effect should enable efficient, large-area and flexible coverage of a heat source. For such applications to be viable, substantial improvements will be necessary not only for their performance but also for the associated material costs, safety and stability. In terms of the electronic structure, the anomalous Nernst effect (ANE) originates from the Berry curvature of the conduction electrons near the Fermi energy. To design a large Berry curvature, several approaches have been considered using nodal points and lines in momentum space. Here we perform a high-throughput computational search and find that 25 percent doping of aluminium and gallium in alpha iron, a naturally abundant and low-cost element, dramatically enhances the ANE by a factor of more than ten, reaching about 4 and 6 microvolts per kelvin at room temperature, respectively, close to the highest value reported so far. The comparison between experiment and theory indicates that the Fermi energy tuning to the nodal web—a flat band structure made of interconnected nodal lines—is the key for the strong enhancement in the transverse thermoelectric coefficient, reaching a value of about 5 amperes per kelvin per metre with a logarithmic temperature dependence. We have also succeeded in fabricating thin films that exhibit a large ANE at zero field, which could be suitable for designing low-cost, flexible microelectronic thermoelectric generators.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Neuromorphic spintronics

Neuromorphic computing uses brain-inspired principles to design circuits that can perform computational tasks with superior power efficiency to conventional computers. Approaches that use traditional electronic devices to create artificial neurons and synapses are, however, currently limited by the energy and area requirements of these components. Spintronic nanodevices, which exploit both the magnetic and electrical properties of electrons, can increase the energy efficiency and decrease the area of these circuits, and magnetic tunnel junctions are of particular interest as neuromorphic computing elements because they are compatible with standard integrated circuits and can support multiple functionalities. Here, we review the development of spintronic devices for neuromorphic computing. We examine how magnetic tunnel junctions can serve as synapses and neurons, and how magnetic textures, such as domain walls and skyrmions, can function as neurons. We also explore spintronics-based implementations of neuromorphic computing tasks, such as pattern recognition in an associative memory, and discuss the challenges that exist in scaling up these systems.

42 ENGINEERING↗
DOE OSTI2021

Electronic structure of NdO via slow photoelectron velocity-map imaging spectroscopy of NdO –

Electronically excited NdO is a possible product of the chemistry associated with the release of Nd into the ionosphere, and emission from these states may contribute to the observations following such experiments. To better characterize the energetics and spectroscopy of NdO, we report a combined experimental and theoretical study using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled NdO – anions (cryo-SEVI) supplemented by wave function-based quantum-chemical calculations. Using cryo-SEVI, we measure the electron affinity of NdO to be 1.0091(7) eV and resolve numerous transitions to low-lying electronic and vibrational states of NdO that are assigned with the aid of the electronic structure calculations. Additionally, temperature-dependent data suggest contributions from the (2)4.5 state of NdO – residing 2350 cm –1 above the ground anion state. Finally, photodetachment to higher-lying excited states of NdO is also reported, which may help to clarify observations from prior release experiments.

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

Wannier representation of Floquet topological states

A universal feature of topological insulators is that they cannot be adiabatically connected to an atomic limit, where individual lattice sites are completely decoupled. This property is intimately related to a topological obstruction to constructing a localized Wannier function from Bloch states of an insulator. In this work, we generalize this characterization of topological phases toward periodically driven systems. We show that nontrivial connectivity of hybrid Wannier centers in momentum space and time can characterize various types of topology in periodically driven systems, which include Floquet topological insulators, anomalous Floquet topological insulators with micromotion-induced boundary states, and gapless Floquet states realized with topological Floquet operators. In particular, nontrivial time dependence of hybrid Wannier centers indicates impossibility of continuous deformation of a driven system into an undriven insulator, and a topological Floquet operator implies an obstruction to constructing a generalized Wannier function which is localized in real and frequency spaces. Our results pave a way to a unified understanding of topological states in periodically driven systems as a topological obstruction in Floquet states.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Coulomb correlation in noncollinear antiferromagnetic 𝛼-Mn

Here, we discuss the interplay between magnetic and structural degrees of freedom in elemental Mn. The equilibrium volume is shown to be sensitive to magnetic interactions between the Mn atoms. While the standard generalized gradient approximation underestimates the equilibrium volume, a more accurate treatment of the effects of electronic localization and magnetism is found to solve this longstanding problem. Our calculations also reveal the presence of a magnetic phase in strained $\alpha$-Mn that has been reported previously in experiments. This new phase of strained $\alpha$-Mn exhibits a noncollinear spin structure with large magnetic moments.

36 MATERIALS SCIENCE↗
DOE OSTI2020

X Fe 4 Ge 2 ( X = Y , Lu ) and Mn 3 Pt : Filling-enforced magnetic topological metals

Magnetism, coupled with nontrivial band topology, can bring about many interesting and exotic phenomena, so that magnetic topological materials have attracted persistent research interest. However, compared with nonmagnetic topological materials (TMs), the magnetic TMs are less studied, since their magnetic structures and topological phase transitions are usually complex and the first-principles predictions are usually sensitive on the effect of Coulomb interaction. Here we present a comprehensive investigation of XFe 4 Ge 2 (X = Y, Lu) and Mn 3 Pt, and find these materials to be filling-enforced magnetic topological metals. Our first-principles calculations show that XFe 4 Ge 2 (X = Y, Lu) host Dirac points near the Fermi level at high symmetry point S. These Dirac points are protected by $\text{P}\mathcal{T}$ symmetry ($\text{P}$ and $\mathcal{T}$ are inversion and time-reversal transformations, respectively) and a twofold screw rotation symmetry. Moreover, through breaking $\text{P}\mathcal{T}$ symmetry, the Dirac points would split into Weyl nodes. Mn 3 Pt is found to host fourfold degenerate band crossings in the whole high symmetry path of A – Z . We also utilize the GGA + U scheme to take into account the effect of Coulomb repulsion and find that the filling-enforced topological properties are naturally insensitive on U .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Topological orders of monopoles and hedgehogs: From electronic and magnetic spin-orbit coupling to quarks

Topological states of matter are, generally, quantum liquids of conserved topological defects. We establish this by constructing and analyzing topological field theories which introduce gauge fields to describe the dynamics of singularities in the original field configurations. In this work, homotopy groups are utilized to identify topologically protected singularities, and the conservation of their protected number is captured by a topological action term that unambiguously obtains from the given set of symmetries. Stable phases of these theories include quantum liquids with emergent massless Abelian and non-Abelian gauge fields, as well as topological orders with long-range quantum entanglement, fractional excitations, boundary modes, and unconventional responses to external perturbations. This paper focuses on the derivation of topological field theories and basic phenomenological characterization of topological orders associated with homotopy groups π n (S n ), n ≥ 1 . These homotopies govern monopole and hedgehog topological defects in d = n + 1 dimensions, and enable the generalization of both weakly interacting and fractional quantum Hall liquids of vortices to d > 2 . Hedgehogs have not been in the spotlight so far, but they are particularly important defects of magnetic moments because they can be stimulated in realistic systems with spin-orbit coupling, such as chiral magnets and d = 3 topological materials. We predict topological orders in systems with U(1) × Spin(d) symmetry in which fractional electric charge attaches to hedgehogs. Monopoles, the analogous defects of charge or generic U(1) currents, may bind to hedgehogs via Zeeman effect, or effectively emerge in purely magnetic systems. The latter can lead to spin liquids with different topological orders than that of the resonant valence bond spin liquid. Charge fractionalization of quarks in atomic nuclei is also seen as possibly arising from the charge-hedgehog attachment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗