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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Benchmarking highly entangled states on a 60-atom analogue quantum simulator

Abstract Quantum systems have entered a competitive regime in which classical computers must make approximations to represent highly entangled quantum states 1,2 . However, in this beyond-classically-exact regime, fidelity comparisons between quantum and classical systems have so far been limited to digital quantum devices 2–5 , and it remains unsolved how to estimate the actual entanglement content of experiments 6 . Here, we perform fidelity benchmarking and mixed-state entanglement estimation with a 60-atom analogue Rydberg quantum simulator, reaching a high-entanglement entropy regime in which exact classical simulation becomes impractical. Our benchmarking protocol involves extrapolation from comparisons against an approximate classical algorithm, introduced here, with varying entanglement limits. We then develop and demonstrate an estimator of the experimental mixed-state entanglement 6 , finding our experiment is competitive with state-of-the-art digital quantum devices performing random circuit evolution 2–5 . Finally, we compare the experimental fidelity against that achieved by various approximate classical algorithms, and find that only the algorithm we introduce is able to keep pace with the experiment on the classical hardware we use. Our results enable a new model for evaluating the ability of both analogue and digital quantum devices to generate entanglement in the beyond-classically-exact regime, and highlight the evolving divide between quantum and classical systems.

Science & Technology - Other Topics↗
DOE OSTI2025

Glass formation during combinatorial sputtering in binary alloys

Glass formation is a complex phenomenon influenced by thermodynamic and kinetic aspects, which are often controlled by extrinsic contributions. While bulk metallic glasses are typically multicomponent alloys, binary alloys offer a simplified approach to studying glass formation. In this study, we fabricated 57 binary alloy systems through combinatorial sputtering, where each alloy system is represented in 66 different alloys. We developed an automated analysis to determine structure and composition using X-ray diffraction and energy-dispersive X-ray spectroscopy for over 3700 alloys. We found that ∼17 % of the alloys form glasses under the estimated cooling rate during sputtering of ∼10 8 K/s. Data analysis revealed that commonly used factors like atomic size ratio and heat of mixing are ineffective in predicting glass formation. However, the crystal structure mismatch of the alloys’ elements emerged as the strongest indicator of glass formation under sputtering conditions of binary alloys. Here, the differences in glass formation under slow cooling rates used for bulk glass formation and the here observed glass formation under rapid cooling rates are discussed.

Binary alloys↗
DOE OSTI2023

Investigating the Electronic Structure of Prospective Water-Splitting Oxide BaCe 0.25 Mn 0.75 O 3-δ before and after Thermal Reduction

BaCe 0.25 Mn 0.75 O 3-δ (BCM), a non-stoichiometric oxide with a layered perovskite-like crystal structure, has recently emerged as a prospective contender for application in renewable energy harvesting by solar thermochemical hydrogen generation. Using solar-thermal energy and a reducing environment, oxygen vacancies can be created in high-temperature BCM, and the reduced crystal so obtained can, in turn, produce H 2 by stripping oxygen from H 2 O. Therefore, a first step toward understanding the working mechanism and optimizing the performance of BCM is a thorough and comparative analysis of the electronic structure of the pristine and the reduced material. In this paper, we probe the electronic structure of BCM using the combined effort of first-principles calculations and experimental O K-edge X-ray absorption spectroscopy (XAS). The computed projected density of states (PDOS) and orbital plots are used to propose a simplified model for orbital mixing between the oxygen and metal atoms. With the help of state-of-the-art simulations, we are able to find the origins of the XAS peaks and categorize them on the basis of contribution from Ce and Mn. For the reduced crystal, the calculations show that the change in electron density resulting from the reduction is strongly localized around the oxygen vacancy. Experimental measurements reveal a marked lowering of the first O K-edge peak in the reduced crystal. Using theoretical analysis, this is shown to result from lifting of spin degeneracy in the absorption peaks as well as from a diminished O 2p contribution to the frontier unoccupied orbitals, in accordance with the tight binding scheme. The simulated results serve as a reference for the extent of spectral change as a function of the percentage of oxygen vacancies in the reduced crystal. Here, our study paves the way for the investigation of the working mechanism of BCM and for computational and experimental efforts aimed at design and discovery of efficient water-splitting oxides.

08 HYDROGEN↗
DOE OSTI2025

Direct measurement of covalent three-center, two-electron M–H–B bonding in Zr and Hf borohydrides using B K-edge XAS

Metal borohydride complexes have long been the subject of intense fundamental interest because of their unconventional metal–ligand bonding that occurs via three-center, two-electron M–H–B bonds. This type of bonding implies significant delocalization of electron density over all three atoms, but the degree of orbital mixing between the metal and boron has been difficult to assess by direct experimental means. Herein, we demonstrate how ligand K-edge X-ray absorption spectroscopy (XAS) conducted at the B K-edge yields evidence of significant covalent M–H–B bonding with Zr and Hf. To accommodate the B K-edge XAS studies, which were conducted under ultra-high vacuum (<10 −8 torr), we prepared a series of new [Zr(RBH 3 ) 4 ] and [Hf(RBH 3 ) 4 ] complexes with substituents that attenuate volatility (R = benzyl, phenyl, mesityl, 2,4,6-triisopropylphenyl, and anthryl). 1 H and 11 B NMR spectroscopy, IR spectroscopy, and single-crystal X-ray diffraction (XRD) studies revealed metal and ligand dependent differences in the BH 3 chemical shifts that correlate to changes in M−B distances and select B–H vibrational stretching modes. The B K-edge XAS spectra of the Zr and Hf complexes yielded a pre-edge feature that was assigned as B 1s → M–H–B π* based on comparison to time-dependent density functional theory (TDDFT) calculations. The pre-edge transitions appear due to covalent mixing between boron and the metal, thereby demonstrating how B K-edge XAS can provide direct evidence of covalent three-center, two electron M–H–B bonding in borohydride complexes using boron as a spectroscopic reporter.

Hansen, Hannah M. [University of Iowa, Iowa City, ↗
DOE OSTI2022

Local cation order and ferrimagnetism in compositionally complex spinel ferrites

We present an exploration of a family of compositionally complex cubic spinel ferrites featuring combinations of Mg, Fe, Co, Ni, Cu, Mn, and Zn cations, systematically investigating the average and local atomic structures, chemical short-range order, magnetic spin configurations, and magnetic properties. All compositions result in ferrimagnetic average structures with extremely similar local bonding environments; however, the samples display varying degrees of cation inversion and, therefore, differing apparent bulk magnetization. Additionally, first-order reversal curve analysis of the magnetic reversal behavior indicates varying degrees of magnetic ordering and interactions, including potentially local frustration. Finally, reverse Monte Carlo modeling of the spin orientation demonstrates a relationship between the degree of cation inversion and the spin collinearity. Collectively, these observations correlate with differences in synthesis procedures. This work provides a framework for understanding magnetic behavior reported for “high-entropy spinels,” revealing many are likely compositionally complex oxides with differing degrees of chemical short-range order—not meeting the community established criteria for high or medium entropy compounds. Moreover, this work highlights the importance of reporting complete sample processing histories and investigating local to long-range atomic arrangements when evaluating potential entropic mixing effects and assumed property correlations in high entropy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Accurate CI-MBPT calculation of radiative lifetimes and transition probabilities of neutral lanthanum (La I) odd states with J = 3/2

In this work, an accurate calculation of radiative lifetimes and transition probabilities of the first 21 odd states with a total angular momentum J = 3/2 was performed for La I using configuration-interaction many-body perturbation theory (CI-MBPT). A technique to obtain correct transition amplitudes was devised for pairs of states with substantial mixing that improved the theoretical accuracy. The results were compared to known experimental and theoretical data for the considered transitions. It has been shown that the transition data calculated with CI-MBPT and with corrections for pairs of mixed states are in good agreement with the latest experimental data of Den Hartog et al, 2015 J. Phys. B: At. Mol. Phys. 48, 155 001, better than other theoretical results. The transition data can find many applications in astrophysics, and the CI-MBPT formalism with mixing correction is applicable to other atoms similar to or more complex than La I.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Compact fiber-coupled narrowband two-mode squeezed light source

Quantum correlated states of light, such as squeezed states, are a fundamental resource for the development of quantum technologies, as they are needed for applications in quantum metrology, quantum computation, and quantum communications. It is thus critical to develop compact, efficient, and robust sources to generate such states. Here, we report on a compact, narrowband, fiber-coupled source of two-mode squeezed states of light at 795 nm based on four-wave mixing (FWM) in an 85 Rb atomic vapor. The source is designed in a small modular form factor, with two input fiber-coupled beams, the seed and pump beams required for the FWM, and two output fibers, one for each of the modes of the squeezed state. The system is optimized for low pump power (135 mW) to achieve a maximum intensity-difference squeezing of 4.4 dB after the output of fibers at an analysis frequency of 1 MHz. Furthermore, the narrowband nature of the source makes it ideal for atomic-based quantum sensing and quantum networking configurations that rely on atomic quantum memories. Such a source paves the way for a versatile and portable platform for applications in quantum information science.

Jain, Umang [University of Oklahoma, Norman, OK (U↗
DOE OSTI2024

Effective optimization of atomic decoration in giant and superstructurally ordered crystals with machine learning

Crystals with complicated geometry are often observed with mixed chemical occupancy among Wyckoff sites, presenting a unique challenge for accurate atomic modeling. Similar systems possessing exact occupancy on all the sites can exhibit superstructural ordering, dramatically inflating the unit cell size. In this work, a crystal graph convolutional neural network (CGCNN) is used to predict optimal atomic decorations on fixed crystalline geometries. This is achieved with a site permutation search (SPS) optimization algorithm based on Monte Carlo moves combined with simulated annealing and basin-hopping techniques. Our approach relies on the evidence that, for a given chemical composition, a CGCNN estimates the correct energetic ordering of different atomic decorations, as predicted by electronic structure calculations. This provides a suitable energy landscape that can be optimized according to site occupation, allowing the prediction of chemical decoration in crystals exhibiting mixed or disordered occupancy, or superstructural ordering. Verification of the procedure is carried out on several known compounds, including the superstructurally ordered clathrate compound Rb8Ga27Sb16 and vacancy-ordered perovskite Cs2SnI6, neither of which was previously seen during the neural network training. In addition, the critical temperature of an order–disorder phase transition in solid solution CuZn is probed with our SPS routines by sampling site configuration trajectories in the canonical ensemble. This strategy provides an accurate method for determining favorable decoration in complex crystals and analyzing site occupation at unprecedented speed and scale.

Chemistry↗
DOE OSTI2023

Excited-State Dynamics during Primary C–I Homolysis in Acetyl Iodide Revealed by Ultrafast Core-Level Spectroscopy

In typical carbonyl-containing molecules, bond dissociation events follow initial excitation to $nπ_{C=O}$$^*$ states. However, in acetyl iodide, the iodine atom gives rise to electronic states with mixed $nπ_{C=O}$$^*$ and $nπ_{C–I}$$^*$ character, leading to complex excited-state dynamics, ultimately resulting in dissociation. Using ultrafast extreme ultraviolet (XUV) transient absorption spectroscopy and quantum chemical calculations, we present an investigation of the primary photodissociation dynamics of acetyl iodide via time-resolved spectroscopy of core-to-valence transitions of the I atom after 266 nm excitation. The probed I 4d-to-valence transitions show features that evolve on sub-100-fs time scales, reporting on excited-state wavepacket evolution during dissociation. These features subsequently evolve to yield spectral signatures corresponding to free iodine atoms in their spin–orbit ground and excited states with a branching ratio of 1.1:1 following dissociation of the C–I bond. Calculations of the valence excitation spectrum via equation-of-motion coupled cluster with single and double substitutions (EOM-CCSD) show that initial excited states are of spin-mixed character. From the initially pumped spin-mixed state, we use a combination of time-dependent density functional theory (TDDFT)-driven nonadiabatic ab initio molecular dynamics and EOM-CCSD calculations of the N$_{4,5}$ edge to reveal a sharp inflection point in the transient XUV signal that corresponds to rapid C–I homolysis. Here, by examining the molecular orbitals involved in the core-level excitations at and around this inflection point, we are able to piece together a detailed picture of C–I bond photolysis in which d → σ* transitions give way to d → p excitations as the bond dissociates. We also report theoretical predictions of short-lived, weak 4d → 5d transitions in acetyl iodide, validated by weak bleaching in the experimental transient XUV spectra. This joint experimental–theoretical effort has thus unraveled the detailed electronic structure and dynamics of a strongly spin–orbit coupled system.

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

Titanium-, Nitrogen-Doped Carbon Flowers Catalyze Electrochemical Nitrate Reduction Reaction to Ammonia

An emerging design heuristic for electrochemical nitrate reduction (NO 3 RR) catalysts is synthesizing electron-deficient sites to facilitate binding of electron-rich NO 3 – . However, this rule has rarely been applied to metal-, nitrogen-doped carbon (MNC) catalysts. Titanium (Ti), with low electronegativity and high NO 3 RR reactivity, is a compelling MNC candidate. To date, atomically dispersed TiN x motifs have eluded synthesis due to the strong oxophilicity of Ti. Here, in this work, we leverage nitrogen-rich carbon flowers (CF) to overcome synthetic challenges and produce Ti-, N-doped carbon flower (TiCF) catalysts. Advanced materials characterization demonstrates that TiCF catalysts are a mixed phase material with 3/4 of Ti atoms in TiO 2 -like nanoparticles and 1/4 of Ti atoms in novel, atomically dispersed TiN x sites. TiCF achieves 61 ± 7% NH 3 -selectivity at −0.70 V vs RHE and 14 ± 5 mA/cm 2 to NH 3 formation (| j NH 3 |) at −0.85 V vs RHE in (0.1 M NaOH + 0.1 M NaNO 3 + 0.45 M Na 2 SO 4 ) electrolyte. Control studies show both CF morphology and Ti sites are essential for high NO 3 RR activity. Density functional theory calculations attribute the NO3RR reactivity to TiN x , which facilitates multiple bond formation with surface intermediates to promote favorable NH3 synthesis pathways. Thus, TiCF exhibits 60× higher | j NH 3 | values than bulk Ti and NH 3 yield rates (>0.06 mmol NH 3 /h/cm 2 ) that are competitive with state-of-the-art MNC catalysts (e.g., FeNC, CuNC). TiCF introduces a new class of Ti electrocatalysts, advancing the MNC design space and sustainable NH 3 production.

ammonia↗
DOE OSTI2025

Crystal structure and magnetic properties of CeFe 11 M (M = Mo, W)

Tetragonal CeFe 11 Mo (struct. type ThMn 12 , a = 8.529(1) Å, c = 4.766(1) Å, V = 346.68(1) Å 3 ) and novel isostructural CeFe 11 W (a = 8.539(1) Å, c = 4.754(1) Å, V = 346.62(1) Å 3 ) are obtained in bulk, as homogenized single-phase arc-melted alloys. Here, their crystal structures are evaluated by full profile Rietveld analysis of the powder X-ray diffraction patterns which confirm that Ce occupies the 2a atomic site in both cases, whereas atomic disorder is present in the Fe-sublattice, i.e., predominantly on the dumbbell 8i site and minorly on two other sites 8j and 8f. In CeFe 11 Mo the third element, M, is mixed with Fe on the 8i dumbbell site and 8f atomic position, whereas in CeFe 11 W, M is mixed on the 8i and 8j Fe sites. In these bulk CeFe 12-x M x alloys the tetragonal structure persists at lower M content, x < 1 here, in comparison to known similar alloys, with x > 1. Because of the low M content, comparably higher values of mass magnetization and Curie temperature are achieved i.e., CeFe 11 Mo: ϭ s = 104 emu/g (14.7 µ B /f.u.), T c = 420 K and CeFe 11 W: ϭ s = 99 emu/g (16.5 µ B /f.u.), T c = 450 K. Magnetocrystalline anisotropy is uniaxial with anisotropy fields H a ∼ 14.5 and 16.5 kOe, respectively. Based on Curie temperature and magnetic anisotropy enhancements, using tungsten as the stabilizing dopant is more beneficial than molybdenum.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Heterogeneity in M. tuberculosis β-lactamase inhibition by Sulbactam

Abstract For decades, researchers have elucidated essential enzymatic functions on the atomic length scale by tracing atomic positions in real-time. Our work builds on possibilities unleashed by mix-and-inject serial crystallography (MISC) at X-ray free electron laser facilities. In this approach, enzymatic reactions are triggered by mixing substrate or ligand solutions with enzyme microcrystals. Here, we report in atomic detail (between 2.2 and 2.7 Å resolution) by room-temperature, time-resolved crystallography with millisecond time-resolution (with timepoints between 3 ms and 700 ms) how the Mycobacterium tuberculosis enzyme BlaC is inhibited by sulbactam (SUB). Our results reveal ligand binding heterogeneity, ligand gating, cooperativity, induced fit, and conformational selection all from the same set of MISC data, detailing how SUB approaches the catalytic clefts and binds to the enzyme noncovalently before reacting to a trans- enamine. This was made possible in part by the application of singular value decomposition to the MISC data using a program that remains functional even if unit cell parameters change up to 3 Å during the reaction.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Trends in Siting of Metals in Heterometallic Nd–Yb Metal–Organic Frameworks and Molecular Crystals

Several studies suggest that metal ordering within metal–organic frameworks (MOFs) is important for understanding how MOFs behave in relevant applications; however, these siting trends can be difficult to determine experimentally. To garner insight into the energetic driving forces that may lead to nonrandom ordering within heterometallic MOFs, we employ density functional theory (DFT) calculations on several bimetallic metal–organic crystals composed of Nd and Yb metal atoms. We also investigate the metal siting trends for a newly synthesized MOF. Our DFT-based energy of mixing results suggest that Nd will likely occupy sites with greater access to electronegative atoms and that local homometallic domains within a mixed-metal Nd–Yb system are favored. We also explore the use of less computationally extensive methods such as classical force fields and cluster expansion models to understand their feasibility for large system sizes. Here, this study highlights the impact of metal ordering on the energetic stability of heterometallic MOFs and crystal structures.

energy of mixing↗
DOE OSTI2024

Spectroscopic evidence of spin-state excitation in d-electron correlated semiconductor FeSb 2

Iron antimonide (FeSb 2 ) has been investigated for decades due to its puzzling electronic properties. It undergoes the temperature-controlled transition from an insulator to an ill-defined metal, with a cross-over from diamagnetism to paramagnetism. Extensive efforts have been made to uncover the underlying mechanism, but a consensus has yet to be reached. While macroscopic transport and magnetic measurements can be explained by different theoretical proposals, the essential spectroscopic evidence required to distinguish the physical origin is missing. In this paper, through the use of X-ray absorption spectroscopy and atomic multiplet simulations, we have observed the mixed spin states of 3d 6 configuration in FeSb 2 . Furthermore, we reveal that the enhancement of the conductivity, whether induced by temperature or doping, is characterized by populating the high-spin state from the low-spin state. Our work constitutes vital spectroscopic evidence that the electrical/magnetical transition in FeSb 2 is directly associated with the spin-state excitation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Energy and mechanical properties predictions in Fe-Ni binary system by ab initio calculations

Here, the fcc random solid solutions in Fe-Ni binary system were investigated using ab initio calculations. Density functional theory (DFT) was applied along with supercells generated by the Special Quasi-Random Structure (SQS) method to predict the enthalpy of mixing and magnetic and elastic properties. The results were compared with relevant experimental and computational data produced by other groups. The effect of SQS supercell size and relaxation procedure on the predicted properties of the alloys were also studied. Our calculations show that 16-atoms SQS model provides adequate approach to the mixing energy of the alloy. However, calculation of mechanical properties requires larger supercell. Excellent agreement between experimental and calculated elastic properties was found in fcc region of Fe-Ni system.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Unveiling the interaction of nanopatterned void superlattices with irradiation cascades

Nanopatterned microstructures in materials can have a profound impact on materials’ physical and chemical properties. While voids are typically considered as detrimental defects in irradiated materials, the patterning of nanoscale voids causes the formation of void superlattices and provides a highly efficient mechanism for gas storage. Despite the important applications of nanopatterned defect superlattices, how they degrade under irradiation remains unclear. Here we provide direct observation of the evolution of void superlattices under irradiation and elucidate the interaction of void superlattices with irradiation cascades. We reveal that the instability of void superlattices under irradiation is caused by heterogenous void shrinkage and demonstrate the imperative role of mixed 1D/3D diffusion of self-interstitial atoms and injected inert gas atoms on void shrinkage and void superlattice instability. Understanding the degradation mechanisms of nanopatterned microstructures is essential to designing damage-tolerant materials and broadening their applications in extreme environments.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Structural Phase Transitions in the van der Waals Ferromagnets Fe x Pd y Te 2

Two-dimensional van der Waals (vdW) magnets are attracting significant attention, both as platforms for studying fundamental magnetic interactions and for the exciting possibility of utilizing them as building blocks in devices and heterostructures, which may lead to new physical phenomena and functionalities. Here, we provide a detailed study of the crystal structure and physical properties of the recently discovered vdW ferromagnet FePd 2 Te 2 . We find this compound has a relatively wide width of formation, and grow single crystals with compositions Fe x Pd y Te 2 where x ranges from 0.9 to 1.1 and y from 1.8 to 2.5, respectively. Temperature-dependent X-ray diffraction and transport measurements reveal that a first-order structural transition occurs in the range of T = 360–420 K, where the critical temperature, modulation wave vector, and corresponding room-temperature crystal structures all depend on chemical composition. Above the transition, the compounds with Pd fraction y > 2 adopt a disordered derivative of the tetragonal FeTe structure, with the Fe layer showing mixed Fe/Pd occupancy and the extra Pd atoms partially occupying interstitial sites. Below 370 K, the structure is incommensurately modulated, likely associated with the complex ordering of Pd/Fe atoms in the metal layers or the interstitial Pd in the vdW gaps. For y < 2, the composition Fe 1.1 Pd 1.8 Te 2 has monoclinic symmetry at room temperature that is consistent with the reported structure of FePd 2 Te 2 . This phase undergoes a structural transition at 420 K for which the high temperature structure is yet to be determined; however, based on the similarities with the y > 2 compounds, we speculate that its T > 420 K structure is also tetragonal. Importantly, the high temperature, symmetry-breaking structural transition observed here provides a likely explanation for the origin of the structural domains previously observed in FePd 2 Te 2 . All compounds investigated in the Fe x Pd y Te 2 series show metallic behavior, with magnetic characterization indicating that they are easy-plane, hard, ferromagnets with T C spanning 98–180 K. Both the critical temperature for the structural transition and the Curie temperature are moderately suppressed with increasing Pd fraction y and corresponding decreasing Fe fraction x, indicating that synthetic control over x and y paves way for the further exploration of these compounds.

crystal structure↗
DOE OSTI2022

Giant Thermoelectric Power Factor Anisotropy in PtSb 1.4 Sn 0.6

In this work, we report on the giant anisotropy found in the thermoelectric power factor (S 2 σ) of marcasite structure-type PtSb 1.4 Sn 0.6 single crystal. PtSb 1.4 Sn 0.6 , synthesized using an ambient pressure flux growth method upon mixing Sb and Sn on the same atomic site, is a new phase different from both PtSb 2 and PtSn 2 , which crystallize in the cubic Pa$\bar{3}$ pyrite and Fm$\bar{3}$m fluorite unit cell symmetry, respectively. The large difference in S 2 σ for heat flow applied along different principal directions of the orthorhombic unit cell stems mostly from anisotropic Seebeck coefficients.

36 MATERIALS SCIENCE↗