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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Ti-6Al-4V to over 1.2 TPa: Shock Hugoniot experiments, ab initio calculations, and a broad-range multiphase equation of state

Titanium alloys are used in a large array of applications. In this work we focus our attention on the most used alloy, Ti-6Al-4V (Ti64), which has excellent mechanical and biocompatibility properties with applications in aerospace, defense, biomedical, and other fields. Here we present high-fidelity experimental shock compression data measured on Sandia’s Z machine. We extend the principal shock Hugoniot for Ti64 to more than threefold compression, up to over 1.2 TPa. We use the data to validate our ab initio molecular dynamics simulations and to develop a highly reliable, multiphase equation of state (EOS) for Ti64, spanning a broad range of temperature and pressures. The first-principles simulations show very good agreement with Z data and with previous three-stage gas gun data from Sandia’s STAR facility. The resulting principal Hugoniot and the broad-range EOS and phase diagram up to 10 TPa and 10 5 K are suitable for use in shock experiments and in hydrodynamic simulations. The high-precision experimental results and high-fidelity simulations demonstrate that the Hugoniot of the Ti64 alloy is stiffer than that of pure Ti and reveal that Ti64 melts on the Hugoniot at a significantly lower pressure and temperature than previously modeled.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Resolving Heterogeneous Dynamics of Excess Protons in Aqueous Solution with Rate Theory

Rate theories have found great utility across the chemical sciences by providing a physically transparent way to analyze dynamical processes. Here we demonstrate the benefits of using transition state theory and Marcus theory to study the rate of proton transfer in HCl solutions. By using long ab initio molecular dynamics simulations we show that good agreement is obtained between these two different formulations of rate theory and how they can be used to study the pathways and life-time of proton transfer in aqueous solution. Since both rate theory formulations utilize identical sets of molecular data, this provides a self-consistent theoretical picture of the rates of aqueous phase proton transfer. Specifically, we isolate and quantify the rates of proton transfer, ion-pair dissociation, and solvent exchange in concentrated HCl solutions. Our analysis predicts a concentration dependence to both proton transfer and ion-pairing. Moreover, our estimate of the life-time for the Zundel species is 0.8 ps and 1.3 ps for 2M and 8M HCl, respectively. In this paper, we demonstrate that concentration effects, can indeed be quantified through the combination of state-of-the-art simulation and theory and provides a picture of the important correlations between the cation (hydronium) and the counter-ion in acid solutions.

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

Pausing ultrafast melting by timed multiple femtosecond-laser pulses

An intense femtosecond-laser excitation of a solid induces highly nonthermal conditions. In materials like silicon, laser-induced bond-softening leads to a highly incoherent ionic motion and eventually nonthermal melting. But is this outcome an inevitable consequence, or can it be controlled? Here, we performed ab initio molecular dynamics simulations of crystalline silicon after timed multiple femtosecond-laser pulse excitations with fluence above the nonthermal melting threshold. Our results demonstrate an excitation mechanism that pauses nonthermal melting and creates a metastable state instead, with an electronic structure similar to the ground state. This mechanism can be generalized to other materials, potentially enabling structural and/or electronic transitions to metastable phases in the high-excitation regime. In addition, our approach could be used to switch off nonthermal contributions in experiments, allowing reliable electron-phonon coupling constants to be obtained more easily.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Thermoelectric performance in disordered Cu 2 ZnSnSe 4 nanostructures driven by ultra-low thermal conductivity

Here, high-energy reactive mechanical alloying (ball milling) was used to synthesize tetragonal and cubic polymorphs of Cu 2 ZnSnSe 4 . The ordered tetragonal (I-4) polymorph undergoes a phase transition above 400 K into a Cu-Zn disordered tetragonal (I-42 m) polymorph, while the cubic (F-43 m) polymorph with full cation disorder is stabilized at room temperature. Both polymorphs show ultra-low thermal conductivities, 0.42 W m -1 K -1 at 722 K and 0.21 W m -1 K -1 at 523 K for the disordered tetragonal and cubic phases respectively. The cubic polymorph has a higher zT in the low-temperature range, peaking at 0.26 (523 K), while the disordered tetragonal has a maximum zT of 0.46 at 712 K. The latter is the highest reported zT for stoichiometric Cu 2 ZnSnSe 4 , comparable to the best-performing doped materials in the literature. A combination of experimental results and ab-initio calculations point to a coupling between structural disorder and microstructure as the mechanism behind the reported performance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electron Energy-Loss Spectroscopy and Differential Phase Contrast Imaging with Active Decision in Multimodal Electron Microscopy: Isotopic detection at the atomic scale

Isotopic engineering provides a powerful route to control phonon behavior in crystalline solids, enabling fundamental studies of lattice dynamics and heat transport at the atomic scale. Here, we directly visualize isotope-dependent phonon propagation in epitaxial Cr 2 O 3 using aberration-corrected scanning transmission electron microscopy (STEM) combined with monochromated, high-energy-resolution electron energy-loss spectroscopy (EELS). Guided by ab initio phonon calculations, we demonstrate that optical phonon modes above 70 meV are predominantly oxygen-derived and exhibit measurable redshifts upon substitution of natural 16 O by enriched 18 O. Spatially resolved vibrational spectrum imaging reveals isotope-enriched tracer layers within Cr 2 O 3 thin films, correlating isotope concentration with phonon intensity variations and vibrational energy shifts. At the nanometer and atomic scales, vibrational EELS mapping uncovers coherent phonon propagation across isotopic interfaces, consistent with theoretical phonon density of states and dispersion relations. These results establish vibrational EELS as a quantitative probe for isotope-dependent phonon transport in materials, opening new possibilities for studying energy dissipation and lattice dynamics.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Solvent structure and dynamics over Brønsted acid MWW zeolite nanosheets

In the liquid phase of heterogeneous catalysis, solvent plays an important role and governs the kinetics and thermodynamics of a reaction. Although it is often difficult to quantify the role of the solvent, it becomes particularly challenging when a zeolite is used as the catalyst. This difficulty arises from the complex nature of the liquid/zeolite interface and the different solvation environments around catalytically active sites. Here, we use ab initio molecular dynamics simulations to probe the local solvation structure and dynamics of methanol and water over MWW zeolite nanosheets with varying Brønsted acidity. We find that the zeolite framework and the number and location of the acid sites in the zeolite influence the structure and dynamics of the solvent. In particular, methanol is more likely to be in the vicinity of the aluminum (Al 3+ ) at the T4 site than at T1 due to easy accessibility. The methanol oxygen binds strongly to the Al at the T4 site, weakening the Al–O for the bridging acid site, which results in the formation of the silanol group, significantly reducing the acidity of the site. The behavior of methanol is in direct contrast to that of water, where protons can easily propagate from the zeolite to the solvent molecules regardless of the acid site location. Furthermore, our work provides molecular-level insights into how solvent interacts with zeolite surfaces, leading to an improved understanding of the catalytic site in the MWW zeolite nanosheet.

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

Ab initio study on fcc Pr with correlation matrix renormalization theory

Here, we studied fcc praseodymium (Pr) with the ab initio correlation matrix renormalization theory (CMRT) explicitly calculating the Coulomb interactions among basis orbitals and without using any adjustable parameters to work for strongly correlated electron systems. We calculated its total energy in a paramagnetic ground state and studied the role of the correlated 4f electrons in the system. Good agreement was obtained between CMRT and experiments in the pressure volume dependence of the fcc phase. We also compared the CMRT results against other theoretical methods including local density approximation + dynamical mean-field theory and showed consistent results among them. Moreover, we found the normalized local charge fluctuation of the 4f electrons as the function of volume exhibits a clear slope change at the volume collapse region, indicating a switch in their correlation nature there.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Glauber-Theory Calculations of High-Energy Nuclear Scattering Observables Using Variational Monte Carlo Wave Functions

Experiments using intermediate- to high-energy radioactive nuclear beams present numerous findings. Extracting important properties of physical observables relies on a firm theoretical analysis. Though Glauber theory is believed to work well, no convincing calculation has so far been done. Here, we perform ab initio Glauber theory calculations of both elastic differential cross sections and total reaction cross sections for p+ 12 C, 12 C+ 12 C, and 6 He+ 12 C systems. The wave functions of both 6 He and 12 C are generated by variational Monte Carlo calculations with spatial and spin-isospin correlations induced by realistic two- and three-nucleon potentials. Glauber’s phase-shift function is computed by Monte Carlo integration up to all orders of nucleon-nucleon multiple scatterings. We show an excellent performance of the Glauber description to the selected data on the above systems. We also find that the cumulant expansion of the phase-shift function converges rapidly up to the second order for the above systems. This finding will open up interesting applications for the analysis of high-energy nuclear experiments.

Horiuchi, W. [Osaka Metropolitan University (Japan↗
DOE OSTI2022

Synthesis and Thermophysical Property Determination of NaCl-PuCl3 Salts

Currently, a knowledge gap exists in the available data and understanding of thermophysical properties relating to fresh fuel salts, especially those containing plutonium. Determination of this data is necessary for the design and construction of test reactors, as well as the licensing of future commercial molten salt reactors. Thermophysical properties such as melting temperature, salt stability, density, and heat capacity were determined on synthesized eutectic NaCl-PuCl3 and a more sodium rich composition containing 25 mol% PuCl3. These measurements document the baseline properties of the salt as a function of temperature for future experiments on irradiated fuel salt which will provide a holistic perspective on the change of thermophysical properties during reactor operations. It was determined that the NaCl-PuCl3 ingot synthesized for this study contained 63.4 mol% NaCl, 36.3 mol% PuCl3, and was 99.7% pure. Upon heating it was shown that the NaCl- PuCl3 eutectic was stable at temperatures of 800°C. The onset of melting occurred at 541°C and the enthalpy of fusion was determined to be 140.7 ± 8.4 J/g. Specific heat capacity measurements showed a slightly decreasing trend with respect to temperature in the liquid phase ranging from 0.67 to 0.57 J/g·K, with an average value of 0.637 ± 0.03 J/g·K (104 ± 5 J/mol·K) between 500 to 720°C. Three independent trials of the molten NaCl-PuCl3 eutectic salt found the density to be ?(T) = 3.8589 – 9.5342·10-4 T(°C), validated between 500 to 800°C. In addition to salt synthesis and experimentally determining thermodynamic properties, Ab Initio molecular dynamic (AIMD) simulations were used to calculate density and heat capacity values.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Machine learning guided discovery of ternary compounds involving La and immiscible Co and Pb elements

Abstract Ternary compounds with an immiscible pair of elements are relatively unexplored but promising for novel quantum materials discovery. Exploring what third element and its ratio that can be added to make stable ternary compounds out of an immiscible pair of elements remains a great challenge. In this work, we combine a machine learning (ML) method with ab initio calculations to efficiently search for the energetically favorable ternary La-Co-Pb compounds containing immiscible elements Co and Pb. Three previously reported structures are correctly captured by our approach. Moreover, we predict a ground state La 3 CoPb compound and 57 low-energy La-Co-Pb ternary compounds. Attempts to synthesize La 3 CoPb via multiple techniques produce mixed or multi-phases samples with, at best, ambiguous signals of the predicted lowest-energy La 3 CoPb and the second lowest-energy La 18 Co 28 Pb 3 phases. The calculated results of Gibbs free energy are consistent with experiments, and will provide very useful guidance for further experimental synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2025

TiSe 2 is a band insulator created by lattice fluctuations, not an excitonic insulator

TiSe 2 is a narrow-gap insulator with a rich array of unique properties. In addition to being a superconductor under certain modifications, it is commonly thought to be a rare realisation of an excitonic insulator. Below 200 K, TiSe 2 undergoes a transition from a high-symmetry ($P\bar{3}m1$) phase to a low-symmetry ($P\bar{3}c1$) charge density wave (CDW). Here we establish that it is indeed an insulator in both $P\bar{3}m1$ and $P\bar{3}c1$ phases. However, the insulating state is driven not by excitonic effects but by symmetry-breaking. In the CDW phase it is static. At high temperature, thermally driven instantaneous deviations from $P\bar{3}m1$ break the symmetry on the characteristic time scale of a phonon. Even though the time-averaged lattice structure assumes $P\bar{3}m1$ symmetry, the time-averaged energy band structure is closer to the CDW phase - a rare instance of a metal-insulator transition induced by dynamical symmetry breaking. We establish these conclusions from quasiparticle self-consistent GW (QSGW) and many-body calculations (QS$G\widehat{W}$), in combination with molecular dynamics simulations to capture the effects of thermal disorder. The many-body theory includes explicitly ladder diagrams in the polarizability, which incorporates excitonic effects in an ab initio manner. We find that the excitonic modification to the potential is weak, ruling out the possibility that TiSe 2 is an excitonic insulator.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Oxidative dehydrogenation of propane on the oxygen adsorbed edges of boron nitride nanoribbons

Metal-free boron nitride has recently been reported to exhibit high catalytic activity and selectivity towards oxidative dehydrogenation of propane (ODHP). Despite several experimental studies, the exact nature and function of the active sites in this emerging catalyst are unknown. In the present work, density functional theory calculations are combined with microkinetic modeling to systematically explore the ODHP on oxygen passivated boron nitride nanoribbons (BNNRs). Here, the relative stabilities of different edge structures of BNNR were examined using ab initio thermodynamic analysis, and the most stable oxygen passivated edge structure was used for a mechanistic study. Microkinetic analysis revealed that a N 2 O or NO x -type active site is active and selective for the conversion of propane to propene. In addition to a heterogeneous catalytic cycle, the proposed N 2 O/NO x -type active sites are expected to be able to generate gas phase C 3 H 7 ˙, which in turn can trigger gas phase reactions of ODHP as experimentally speculated.

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

Ring-Opening Dynamics of the Cyclopropyl Radical and Cation: the Transition State Nature of the Cyclopropyl Cation

Here, we provide compelling experimental and theoretical evidence for the transition state nature of the cyclopropyl cation. Synchrotron photoionization spectroscopy employing coincidence techniques together with a novel simulation based on high-accuracy ab initio calculations reveal that the cation is unstable via its allowed disrotatory ring-opening path. The ring strains of the cation and the radical are similar, but both ring opening paths for the radical are forbidden when the full electronic symmetries are considered. These findings are discussed in light of the early predictions by Longuet-Higgins alongside Woodward and Hoffman; we also propose a simple phase space explanation for the appearance of the cyclopropyl photoionization spectrum. The results of this work allow the refinement of the cyclopropane C–H bond dissociation energy, in addition to the cyclopropyl radical and cation cyclization energies, via the Active Thermochemical Tables approach.

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

How well do one-electron self-interaction-correction methods perform for systems with fractional electrons?

Recently developed locally scaled self-interaction correction (LSIC) is a one-electron SIC method that, when used with a ratio of kinetic energy densities (z σ ) as iso-orbital indicator, performs remarkably well for both thermochemical properties as well as for barrier heights overcoming the paradoxical behavior of the well-known Perdew–Zunger self-interaction correction (PZSIC) method. In this work, we examine how well the LSIC method performs for the delocalization error. Our results show that both LSIC and PZSIC methods correctly describe the dissociation of $H$$^{+}_{2}$ and $H$$^{+}_{2}$ but LSIC is overall more accurate than the PZSIC method. Likewise, in the case of the vertical ionization energy of an ensemble of isolated He atoms, the LSIC and PZSIC methods do not exhibit delocalization errors. For the fractional charges, both LSIC and PZSIC significantly reduce the deviation from linearity in the energy vs number of electrons curve, with PZSIC performing superior for C, Ne, and Ar atoms while for Kr they perform similarly. The LSIC performs well at the endpoints (integer occupations) while substantially reducing the deviation. The dissociation of LiF shows both LSIC and PZSIC dissociate into neutral Li and F but only LSIC exhibits charge transfer from Li + to F – at the expected distance from the experimental data and accurate ab initio data. Overall, both the PZSIC and LSIC methods reduce the delocalization errors substantially.

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

Tuning Point Defects by Elastic Strain Modulates Nanoparticle Exsolution on Perovskite Oxides

Exsolution generates stable and catalytically active metal nanoparticles via phase precipitation out of a host oxide. An ability to control the size and dispersion of the exsolution particles is desirable for design of nanostructured (electro)catalysts. In this work, we demonstrate that tuning point defects by lattice strain affects both the thermodynamics and the kinetics of iron (Fe 0 ) exsolution on La 0.6 Sr 0.4 FeO 3 (LSF) thin film model. By combining in situ surface characterization and ab initio defect modeling, we show oxygen vacancy and Schottky defects to be the primary point defects formed upon Fe0 exsolution. Lattice strain tunes the formation energy, and thus the abundance of these defects, and alters the amount and size of the resulting exsolution particles. In addition, we find that the density of exsolved nanoparticles matches the concentration of oxygen vacancy pairs, thus pointing to the surface oxygen vacancy pairs as preferential nucleation sites for exsolution. The tensile-strained LSF with a facile formation of these critical point defects results in a higher Fe 0 metal concentration, a larger density of nanoparticles, and a reduced particle size at its surfaces. These results provide important mechanistic insights and highlight the role of point-defect engineering in designing nanostructured catalysts in energy and fuel conversion technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2022

High Resolution Photoelectron Spectroscopy of the Acetyl Anion

High-resolution photoelectron spectra of cryogenically cooled acetyl anions (CH 3 CO - ) obtained using slow photoelectron velocity-map imaging are reported. The high resolution of the photoelectron spectrum yields a refined electron affinity of 0.4352 ± 0.0012 eV for the acetyl radical as well as the observation of a new vibronic structure that is assigned based on ab initio calculations. Three vibrational frequencies of the neutral radical are measured to be 1047 ± 3 cm -1 (ν 6 ), 834 ± 2 cm -1 (ν 7 ), and 471 ± 1 cm -1 (ν 8 ). Here this work represents the first experimental measurement of the ν 6 frequency of the neutral. The measured electron affinity is used to calculate a refined value of 1641.35 ± 0.42 kJ mol -1 for the gas-phase acidity of acetaldehyde. Analysis of the photoelectron angular distributions provides insight into the character of the highest occupied molecular orbital of the anion, revealing a molecular orbital with strong d-character. Additionally, details of a new centroiding algorithm based on finite differences, which has the potential to decrease data acquisition times by an order of magnitude at no cost to accuracy, are provided.

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

Spin-resolved topology and partial axion angles in three-dimensional insulators

Abstract Symmetry-protected topological crystalline insulators (TCIs) have primarily been characterized by their gapless boundary states. However, in time-reversal- ( $${{{{{{{\mathcal{T}}}}}}}}$$ T -) invariant (helical) 3D TCIs—termed higher-order TCIs (HOTIs)—the boundary signatures can manifest as a sample-dependent network of 1D hinge states. We here introduce nested spin-resolved Wilson loops and layer constructions as tools to characterize the intrinsic bulk topological properties of spinful 3D insulators. We discover that helical HOTIs realize one of three spin-resolved phases with distinct responses that are quantitatively robust to large deformations of the bulk spin-orbital texture: 3D quantum spin Hall insulators (QSHIs), “spin-Weyl” semimetals, and $${{{{{{{\mathcal{T}}}}}}}}$$ T -doubled axion insulator (T-DAXI) states with nontrivial partial axion angles indicative of a 3D spin-magnetoelectric bulk response and half-quantized 2D TI surface states originating from a partial parity anomaly. Using ab-initio calculations, we demonstrate that β -MoTe 2 realizes a spin-Weyl state and that α -BiBr hosts both 3D QSHI and T-DAXI regimes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

A Surface Se-Substituted LiCo[O 2-δ Se δ ] Cathode with Ultrastable High-Voltage Cycling in Pouch Full-Cells

Cycling LiCoO 2 to above 4.5 V for higher capacity is enticing; however, hybrid O anion- and Co cation-redox (HACR) at high voltages facilitates intrinsic O α - (α < 2) migration, causing oxygen loss, phase collapse, and electrolyte decomposition that severely degrade the battery cyclability. Hereby, commercial LiCoO 2 particles are operando treated with selenium, a well-known anti-aging element to capture oxygen-radicals in the human body, showing an “anti-aging” effect in high-voltage battery cycling and successfully stopping the escape of oxygen from LiCoO 2 even when the cathode is cycled to 4.62 V. Furthermore, ab initio calculation and soft X-ray absorption spectroscopy analysis suggest that during deep charging, the precoated Se will initially substitute some mobile O α - at the charged LiCoO 2 surface, transplanting the pumped charges from O α - and reducing it back to O 2- to stabilize the oxygen lattice in prolonged cycling. As a result, the material retains 80% and 77% of its capacity after 450 and 550 cycles under 100 mA g -1 in 4.57 V pouch full-cells matched with a graphite anode and an ultralean electrolyte (2 g Ah -1 ).

36 MATERIALS SCIENCE↗