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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Revisit the VEC criterion in high entropy alloys (HEAs) with high-throughput ab initio calculations: A case study with Al-Co-Cr-Fe-Ni system

Valence electron concentration (VEC) was treated as a useful parameter to predict the stability of solid solution phases. However, the available experimental data to support this criterion is far from enough. In the current study, the high-throughput ab initio modeling is applied to investigate the relative stability of FCC and BCC single crystals of the Al-Co-Cr-Fe-Ni high entropy alloys (HEAs) by using the special quasi-random structure (SQS) approach. Furthermore, the predictions start with pure elements of the Al-Co-Cr-Fe-Ni system and are continued with binaries, ternaries, and quaternary compositions, which come up with 180 compositions (360 structures). After that, the reliability of the VEC criterion is testified. The results show that the VEC criterion not only works for the stable structure but also works effectively for metastable structure when both FCC and BCC are not thermodynamic stable. However, it is found that the old VEC criterion proposed by Guo et al. fails to work effectively for compositions containing high concentrations of light-weight metals such as Al at VEC<5. To solve this problem, the present work proposes a new VEC rule to define the stability of FCC and BCC structures at the ground state. With the implementation of the new VEC rule, the effectiveness of the VEC rule (EVEC) of both FCC and BCC structures is enhanced, especially for pure elements and binary compositions, indicating that this rule does not only work effectively for multicomponent systems but also works for low-order systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cumulant methods for electron-phonon problems. I. Perturbative expansions

Here in this work, we investigate the ability of the cumulant expansion (CE) to capture one-particle spectral information in electron-phonon coupled systems at both zero and finite temperatures. In particular, we present a comprehensive study of the second- and fourth-order CEs for the one-dimensional Holstein model as compared with numerically exact methods. We investigate both finite sized systems as well as the approach to the thermodynamic limit, drawing distinctions, and connections between the behavior of systems in and away from the thermodynamic limit that enable a greater understanding of the ability of the CE to capture real-frequency information across the full range of wave vectors. We find that for zero electronic momentum, the spectral function is well described by the second-order CE at low and high temperatures. However, for nonzero electronic momenta, the CE is only accurate at high temperature. We analyze the fourth-order cumulant and find that while it improves the description of the short-time dynamics encoded in the one-particle Green's function, it can introduce divergences in the time domain as well as unphysical negative spectral weight in the spectral function. When well-behaved, the fourth-order CE does provide notable accurate corrections to the second-order CE. Finally, we use our results to comment on the use of the CE as a tool for calculating transport behavior in the realistic ab initio modeling of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

ATOMIC Simulations and Experimental Data for CaCO3 Mixtures

This data consists of simulations and experimental measurements of laser-induced breakdown spectroscopy (LIBS). The simulations are produced by ATOMIC, a general purpose plasma modeling and kinetics code that has been designed to compute emission (or absorption) spectra from plasmas [1] and are used to develop a statistical characterization of matrix effects. Our overall suite of simulations includes contains several sets of simulations: training and validation sets of simulations for three and four element mixtures of calcium, carbon, oxygen, and nitrogen (included to account for atmosphere) along with simulations of the individual elements. The 4-element simulations include the mixture of all four elements mentioned and for each of the four individual elements. The 3-element simulations include output for the mixture of calcium, carbon, oxygen and for these three individual elements. The training data were produced using a 600-run design, shown in Figure 1, that varies input parameters temperature (T), electron density (Ne), and proportion of the elements calcium, carbon, oxygen, and nitrogen (Ca; C; O; N) for the 4 element output. The 3-element output includes all parameters except for the proportion of nitrogen. The element proportions (all the variables but T and Ne) sum to one and are unused in the single-element simulations. The validation data was produced with a 80-run design shown in Figure 2. The training and validation simulation outputs for the 4-element simulations for the mixture and for the single element calcium are shown as sample simulations in Figures 3 and 4 respectively. The simulations produce spectra over a range of 190nm - 950nm that roughly mimics the range collected by the SciAps Z-300 LIBS instrument that was used for the experimental data. The measured spectra for a CaCO3 (which may include contribution from Earth's atmosphere) in the experiment is shown in in Figure 5. All files are kept in directories whose names indicate the elemental composition (CaCO3, Ca, C, O, or N), number of elements (3 or 4), and purpose (training, which is not labeled in the file name, or validation) with file names numbered to indicate the line in the design files used to produce the simulation. The designs are provided as text files with names indicating their purpose. The experimental data is provided as a CSV file. [1] J Colgan, EJ Judge, DP Kilcrease, and JE Barefield II. Ab-initio modeling of an iron laser-induced plasma: Comparison between theoretical and experimental atomic emission spectra. Spectrochimica Acta Part B: Atomic Spectroscopy, 97:65{73}, 2014.

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

Ab initio quantum dynamics of plasmonic charge carriers

Surface plasmons respond strongly to electric fields and generate energetic (hot) charge carriers that can be used in optoelectronic devices. However, utilization of hot carriers has to outcompete fast carrier relaxation in metals. Often, the reported efficiencies of nanoscale devices based on plasmon excitations are low and the mechanisms of device operation remain inconsistent within the field. Further developments hinge on fundamental understanding of the nature and kinetics of plasmon decay processes. In this work, we provide an overview of time domain ab initio modeling of hot carrier dynamics, demonstrating that atomistic details of the surface structure of plasmonic materials, and their chemical interaction with semiconducting and molecular charge acceptors and substrates, play key roles in governing the dynamics pathways. Considered case studies represent various dynamics channels and illustrate solar energy and optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Smaller Is Better: The Case for Lower-Order Iodoplumbate Species Dominating MAPbI 3 /Dimethylformamide Solutions

Here, using complementary experimental measurements and computational predictions of spectroscopic measurements (EXAFS, XANES, and UV–vis), we have determined the identity of the most stable iodoplumbate species in dilute lead halide perovskite precursor solutions. We have determined which species are most likely to be thermodynamically stable compared to others that are unstable or metastable. Condensed phase ab initio models were constructed, and the resulting ensembles were used to directly compare the computed signals to the experimental results of the EXAFS, XANES, and UV–vis spectra of PbI 2 :MAI in DMF. The results of this study suggest that only Pb 2+ , PbI + , and PbI 2 are dominant in the dilute lead perovskite precursor solutions as thermodynamically stable entities. Our interpretation of the relative stability of iodoplumbate species in solution, based on an analysis of EXAFS and XANES spectra, provides critically important new insight into the species most likely to be responsible for crystal nucleation and growth in these materials. This insight will have a significant consequence on the broad scientific community and will necessitate the reinterpretation of peaks in the UV–vis spectra of lead halide perovskite precursor solutions.

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

Nucleation Rate Theory for Coordination Number: Elucidating Water-Mediated Formation of a Zigzag Na 2 SO 4 Morphology

Predicting and controlling nanostructure formation during nucleation can pave the way to synthesizing novel energy materials via crystallization. However, such control over nucleation and crystallization remains challenging due to an inadequate understanding of critical factors that govern evolving atomistic structures and dynamics. Here, in this paper, we utilize coordination number as a reaction coordinate and rate theory to investigate how sodium sulfate, commonly known as a phase-change energy material, nucleates in a supersaturated aqueous solution. In conjunction with ab initio and force field-based molecular dynamics simulation, the rate theoretical analysis reveals that sodium sulfate from an initially dissolved metastable state transits to a heterogeneous mixture of prenucleated clusters and finally to a large cylindrical zigzag morphology. Measurements of Raman spectra and their ab initio modeling confirm that this nucleated morphology contains a few waters for every sulfate. Rate processes such as solvent exchange and desolvation exhibit high sensitivity to the evolving prenucleation/nucleation structures, providing a means to distinguish between critical nucleation precursors. Desolvation and forming the first-shell interionic coordination structure via monomer-by-monomer addition around sulfates are found to explain the formation of large nuclei. Thus, a detailed understanding of the step-by-step structure formation across scales has been achieved. This can be leveraged to predict nucleation-related structures and dynamics and potentially control the synthesis of novel phase-change materials for energy applications.

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

Nanoscale and Element-Specific Lattice Temperature Measurements Using Core-Loss Electron Energy-Loss Spectroscopy

Measuring nanoscale local temperatures, particularly in vertically integrated and multicomponent systems, remains challenging. Spectroscopic techniques like X-ray absorption and core-loss electron energy-loss spectroscopy (EELS) are sensitive to lattice temperature, but understanding thermal effects is nontrivial. This work explores the potential for nanoscale and element-specific core-loss thermometry by comparing the Si L2,3 edge’s temperature- dependent redshift against plasmon energy expansion thermometry (PEET) in a scanning TEM. Using density functional theory (DFT), time-dependent DFT, and the Bethe−Salpeter equation, we ab initio model both the Si L 2,3 and plasmon redshift. We find that the core-loss redshift occurs due to bandgap reduction from electron−phonon renormalization. Our results indicate that despite lower core-loss signal intensity compared to plasmon features, core-loss thermometry has key advantages and can be more accurate through standard spectral denoising. Specifically, we show that the Varshni equation easily interprets the core-loss redshift for semiconductors, which avoids plasmon spectral convolution for PEET in complex junctions and interfaces. We also find that core-loss thermometry is more accurate than PEET at modeling thermal lattice expansion in semiconductors, unless the specimen’s temperature-dependent dielectric properties are fully characterized. Furthermore, core-loss thermometry has the potential to measure nanoscale heating in multicomponent materials and stacked interfaces with elemental specificity at length scales smaller than the plasmon’s wave function.

Bethe–Salpeter equation↗
DOE OSTI2020

Porous Ti-MOF-74 Framework as a Strong-Binding Nitric Oxide Scavenger

Combining synthesis, infrared spectroscopy, and ab initio modeling we show that the titanium-based porous framework Ti-MOF-74 has potential as an environmental nitric oxide (NO) scavenger, exhibiting an extraordinarily strong binding affinity and selectivity over other flue-gas components. The robustness upon exposure to water vapor and high flue-gas stack temperatures suggests that this material can perform well in an industrial environment. In-depth analysis of the Ti-NO bond indicates that the NO forms a strong covalent bond with the Ti. The process of this NO bond formation involves a reaction with the OH- capping groups of the Ti to form NO x groups, after which the excess NO binds to the open Ti metal sites. Ti-MOF-74 thus becomes, to the best of our knowledge, the first known porous framework that binds NO significantly stronger than water, providing novel avenues for environmental and physiological scavenging applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Magnetically Induced Binary Ferrocene with Oxidized Iron

Ferrocene is perhaps the most popular and well-studied organometallic molecule, but our understanding of its structure and electronic properties has not changed for more than 70 years. In particular, all previous attempts of chemically oxidizing pure ferrocene by binding directly to the iron center have been unsuccessful, and no significant change in structure or magnetism has been reported. Here, using a metal organic framework host material, we were able to fundamentally change the electronic and magnetic structure of ferrocene to take on a never-before observed physically stretched/bent high-spin Fe(II) state, which readily accepts O 2 from air, chemically oxidizing the iron from Fe(II) to Fe(III). We also show that the binding of oxygen is reversible through temperature swing experiments. Our analysis is based on combining Mößbauer spectroscopy, extended X-ray absorption fine structure, in situ infrared, SQUID, thermal gravimetric analysis, and energy dispersive X-ray fluorescence spectroscopy measurements with ab initio modeling.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Designing lithium halide solid electrolytes

All-solid-state lithium batteries have attracted widespread attention for next-generation energy storage, potentially providing enhanced safety and cycling stability. The performance of such batteries relies on solid electrolyte materials; hence many structures/phases are being investigated with increasing compositional complexity. Among the various solid electrolytes, lithium halides show promising ionic conductivity and cathode compatibility, however, there are no effective guidelines when moving toward complex compositions that go beyond ab -initio modeling. Here, we show that ionic potential, the ratio of charge number and ion radius, can effectively capture the key interactions within halide materials, making it possible to guide the design of the representative crystal structures. This is demonstrated by the preparation of a family of complex layered halides that combine an enhanced conductivity with a favorable isometric morphology, induced by the high configurational entropy. This work provides insights into the characteristics of complex halide phases and presents a methodology for designing solid materials.

25 ENERGY STORAGE↗
DOE OSTI2025

Pomeranchuk instability from electronic correlations in CsTi 3 Bi 5 kagome metal

Electronic nematicity, the spontaneous breaking of rotational symmetry, has emerged as a key instability in correlated quantum systems. CsTi 3 Bi 5 , a kagome metal of the AV 3 Sb 5 (A = K, Rb, Cs) family, hosts rich unconventional electronic phases, yet the origin of its nematicity remains unsettled. Here, we combine polarization-dependent angle-resolved photoemission spectroscopy with functional renormalization group calculations on a fully interacting ab initio model. We reveal an orbital-selective nematic deformation in the low-energy band structure and identify a finite angular momentum (d-wave) Pomeranchuk instability driven by electronic correlations in specific orbital channels and detuning from Van Hove singularities. Our results establish a direct link between orbital selectivity and symmetry-breaking instabilities in CsTi 3 Bi 5 , providing a microscopic framework for nematic order in kagome systems.

Bigi, Chiara [Synchrotron SOLEIL, Saint-Aubin (Fra↗
DOE OSTI2023

The structure and electronic properties of tetrahedrally bonded hydrogenated amorphous carbon

In this work, we have synthesized hydrogenated and deuterated amorphous carbon materials that have a density, 2.7 ± 0.1 g/cm 3 , consistent with almost entirely tetrahedral bonding. In hydrogen-free tetrahedral amorphous carbon, the presence of a minority of sp2 bonded atoms leads to localized states that could be passivated with hydrogen by analogy with hydrogenated amorphous silicon. Neutron diffraction analysis demonstrated that the local bonding environment is consistent with ab initio models of high density hydrogenated tetrahedral amorphous carbon and with the related tetrahedral molecular structure neopentane. The optical bandgap of our material, 4.5 eV, is close to the bandgap in the density of states determined by scanning tunneling spectroscopy (4.3 eV). This bandgap is considerably larger than that of hydrogen-free tetrahedral amorphous carbon, confirming that passivation of sp 2 associated tail-states has occurred. Both the structural and electronic measurements are consistent with a model in which the tetrahedrally bonded carbon regions are terminated by hydrogen, causing hopping conductivity to dominate.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Minimizing the diffusivity difference between vacancies and interstitials in multi-principal element alloys

Interstitial atoms usually diffuse much faster than vacancies, which is often the root cause for the ineffective recombination of point defects in metals under irradiation. Here, via ab initio modeling of single-defect diffusion behavior in the equiatomic NiCoCrFe(Pd) alloy, we demonstrate an alloy design strategy that can reduce the diffusivity difference between the two types of point defects. The two diffusivities become almost equal after substituting the NiCoCrFe base alloy with Pd. The underlying mechanism is that Pd, with a much larger atomic size (hence larger compressibility) than the rest of the constituents, not only heightens the activation energy barrier ( E a ) for interstitial motion by narrowing the diffusion channels but simultaneously also reduces E a for vacancies due to less energy penalty required for bond length change between the initial and the saddle states. Our findings have a broad implication that the dynamics of point defects can be manipulated by taking advantage of the atomic size disparity, to facilitate point-defect annihilation that suppresses void formation and swelling, thereby improving radiation tolerance.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Importance of van der Waals interactions for ab initio studies of topological insulators

We investigate the lattice and electronic structures of the bulk and surface of the prototypical layered topological insulators Bi 2 Se 3 and Bi 2 Te 3 using ab initio density functional methods, and systematically compare the results of different methods of including van der Waals (vdW) interactions. We show that the methods utilizing semi-empirical energy corrections yield accurate descriptions of these materials, with the most precise results obtained by properly accounting for the long-range tail of the vdW interactions. The bulk lattice constants, distances between quintuple layers and the Dirac velocity of the topological surface states (TSS) are all in excellent agreement with experiment. In Bi 2 Te 3 , hexagonal warping of the energy dispersion leads to complex spin textures of the TSS at moderate energies, while in Bi 2 Se 3 these states remain almost perfectly helical away from the Dirac point, showing appreciable signs of hexagonal warping at much higher energies, above the minimum of the bulk conduction band. Furthermore, our results establish a framework for unified and systematic self-consistent first principles calculations of topological insulators in bulk, slab and interface geometries, and provides the necessary first step toward ab initio modeling of topological heterostructures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Machine learning of hidden variables in multiscale fluid simulation

Solving fluid dynamics equations often requires the use of closure relations that account for missing microphysics. For example, when solving equations related to fluid dynamics for systems with a large Reynolds number, sub-grid effects become important and a turbulence closure is required, and in systems with a large Knudsen number, kinetic effects become important and a kinetic closure is required. By adding an equation governing the growth and transport of the quantity requiring the closure relation, it becomes possible to capture microphysics through the introduction of ‘hidden variables’ that are non-local in space and time. The behavior of the ‘hidden variables’ in response to the fluid conditions can be learned from a higher fidelity or ab-initio model that contains all the microphysics. In our study, a partial differential equation simulator that is end-to-end differentiable is used to train judiciously placed neural networks against ground-truth simulations. We show that this method enables an Euler equation based approach to reproduce non-linear, large Knudsen number plasma physics that can otherwise only be modeled using Boltzmann-like equation simulators such as Vlasov or particle-in-cell modeling.

42 ENGINEERING↗
DOE OSTI2022

Deformed spin- 1 2 square lattice in antiferromagnetic NaZnVOPO 4 ( HPO 4 )

In this work, we report the structural and magnetic properties of a new spin-$\frac{1}{2}$ antiferromagnet NaZnVOPO 4 (HPO 4 ) studied via x-ray diffraction, magnetic susceptibility, high-field magnetization, specific heat, and 31 P nuclear magnetic resonance (NMR) measurements, as well as density-functional band-structure calculations. While thermodynamic properties of this compound are well described by the J 1 – J 2 square-lattice model, ab initio calculations suggest a significant deformation of the spin lattice. From fits to the magnetic susceptibility we determine the averaged nearest-neighbor and second-neighbor exchange couplings of $\bar{J}$ 1 ≃ – 1.3 K and $\bar{J}$ 2 ≃ 5.6 K , respectively, resulting in the effective frustration ratio α = $\bar{J}$ 2 – $\bar{J}$ 1 ≃ – 4.3 that implies columnar antiferromagnetic order as the ground state. Experimental saturation field of 15.3 T is consistent with these estimates if 20% spatial anisotropy in J 1 is taken into account. Specific heat data signal the onset of a magnetic long-range order at T N ≃ 2.1 K , which is further supported by a sharp peak in the NMR spin-lattice relaxation rate. The NMR spectra mark the superposition of two P lines due to two nonequivalent P sites where the broad line with the strong hyperfine coupling and short T 1 is identified as the P(1) site located within the magnetic planes, while the narrow line with the weak hyperfine coupling and long T 1 is designated as the P(2) site located between the planes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Particle-hole asymmetric phases in doped twisted bilayer graphene

Twisted bilayer graphene (TBG) has emerged as a paradigmatic platform for exploring the interplay between strong interactions in a multi-band system with nearly flat bands, while offering unprecedented control over the filling fraction of electron/hole carriers. Despite much theoretical work, developing a comprehensive ab initio model for this system has proven challenging due to the inherent trade-off between accurately describing the band structure and incorporating the interactions within the Hamiltonian. Here, we constructed an extended multi-orbital Hubbard model, and performed Hartree-Fock (HF) calculations to explore its phase diagram across commensurate fillings. We found several nearly-degenerate insulating states at charge neutrality, all of which exhibit orbital orders. We also observed that most of the Hartree–Fock ground states exhibit a generalized valley Hund’s-like rule, resulting in valley polarization. Importantly, we show that the incorporation of the intra-valley and inter-valley exchange interactions is crucial to properly stabilize the ordered symmetry-broken states. In agreement with experiments, we find significant particle-hole asymmetry, which underscores the importance of using particle-hole asymmetric models.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

High-Precision Spectroscopy of 20 O Benchmarking Ab Initio Calculations in Light Nuclei

The excited states of unstable 20 O were investigated via γ-ray spectroscopy following the 19 O(d, p) ⁢20 O reaction at 8 A⁢ MeV. By exploiting the Doppler shift attenuation method, the lifetimes of the $2^+_2$ and $3^+_1$ states were firmly established. From the γ-ray branching and E⁢2/M⁢1 mixing ratios for transitions deexciting the $2^+_2$ and $3^+_1$ states, the B⁡(E⁢2) and B⁡(M⁢1) were determined. Various chiral effective field theory Hamiltonians, describing the nuclear properties beyond ground states, along with a standard USDB interaction, were compared with the experimentally obtained data. Such a comparison for a large set of γ-ray transition probabilities with the valence space in medium similarity renormalization group ab initio calculations was performed for the first time in a nucleus far from stability. It was shown that the ab initio approaches using chiral effective field theory forces are challenged by detailed high-precision spectroscopic properties of nuclei. Finally, the reduced transition probabilities were found to be a very constraining test of the performance of the ab initio models.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗