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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Equation-of-state, sound speed, and reshock of shock-compressed fluid carbon dioxide

Mechanical equation-of-state data of initially liquid and solid CO2 shock-compressed to terapascal conditions are reported. Diamond-sapphire anvil cells were used to vary the initial density and state of CO2 samples that were then further compressed with laser-driven shock waves, resulting in a data set from which precise derivative quantities, including Grüneisen parameter and sound speed, are determined. Reshock states are measured to 800 GPa and map the same pressure-density conditions as the single shock using different thermodynamic paths. The compressibility data reported here do not support current density-functional-theory calculations, but are better represented by tabular equation-of-state models.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

The multichannel i -propyl + O2 reaction system: A model of secondary alkyl radical oxidation

The i-propyl + O2 reaction mechanism has been investigated by definitive quantum chemical methods to establish this system as a benchmark for the combustion of secondary alkyl radicals. Focal point analyses extrapolating to the ab initio limit were performed based on explicit computations with electron correlation treatments through coupled cluster single, double, triple, and quadruple excitations and basis sets up to cc-pV5Z. The rigorous coupled cluster single, double, and triple excitations/cc-pVTZ level of theory was used to fully optimize all reaction species and transition states, thus, removing some substantial flaws in reference geometries existing in the literature. The vital i-propylperoxy radical (MIN1) and its concerted elimination transition state (TS1) were found 34.8 and 4.4 kcal mol−1 below the reactants, respectively. Two β-hydrogen transfer transition states (TS2, TS2′) lie above the reactants by (1.4, 2.5) kcal mol−1 and display large Born–Oppenheimer diagonal corrections indicative of nearby surface crossings. An α-hydrogen transfer transition state (TS5) is discovered 5.7 kcal mol−1 above the reactants that bifurcates into equivalent α-peroxy radical hanging wells (MIN3) prior to a highly exothermic dissociation into acetone + OH. The reverse TS5 → MIN1 intrinsic reaction path also displays fascinating features, including another bifurcation and a conical intersection of potential energy surfaces. An exhaustive conformational search of two hydroperoxypropyl (QOOH) intermediates (MIN2 and MIN3) of the i-propyl + O2 system located nine rotamers within 0.9 kcal mol−1 of the corresponding lowest-energy minima.

Chemistry↗
DOE OSTI2025

Disorder driven crossover between anomalous Hall regimes in Fe 3 GaTe 2

The large anomalous Hall conductivity (AHC) of the Fe 3 ⁢(Ge,Ga)⁢Te 2 compounds has attracted considerable attention. Here, we expose the intrinsic nature of the AHC in Fe 3 ⁢GaTe 2 crystals characterized by high conductivities, which show disorder-independent AHC with a pronounced value 𝜎$^{c}_{𝑥⁢𝑦}$≈ 420 Ω −1 ⁢cm −1 . In the low-conductivity regime, we observe the scaling relation 𝜎 𝑥⁢𝑦 ∝ 𝜎$^{1.6}_{𝑥⁢𝑥}$, which crosses over to 𝜎 𝑥⁢𝑦 ≃ 𝜎$^{c}_{𝑥⁢𝑦}$ as 𝜎 𝑥⁢𝑥 increases. Disorder in low-conductivity crystals is confirmed by the broadening of a first-order transition between ferromagnetism and the ferrimagnetic ground state. Through density functional theory (DFT) calculations, we reveal that the dominant sources of Berry curvature are located a few hundred meV below the Fermi energy around the Γ point. Furthermore, Fe 3⁢ GaTe 2 clearly exposes the disorder-induced crossover among distinct AHC regimes, previously inferred from measurements on different ferromagnets located on either side of the crossover region.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Density functional theory investigations into the magnetic ordering of U 3 O 8

Density functional theory (DFT) has been highly successful in supporting experimental materials science; however, a correct electronic ground state is required to realize the full theoretical capacity of DFT. The uranium oxides, α–U 3 O 8 in particular, are simultaneously technologically important materials and theoretically challenging for DFT because the uranium magnetic ground state is not obvious. This is true for both experiment and theory—magnetic susceptibility measurements indicate an antiferromagnetic (AFM) ground state with transitions near 4.2 and 8.0 K, but the ordering itself is not known. Theoretical literature reports are in contradiction, with independent studies finding paramagnetic, ferromagnetic (FM), and AFM states as the lowest energy configuration. However, recent inelastic neutron scattering experiments suggested an uninvestigated magnetic structure with ordering along the [0.5 1 1] plane, motivating a theoretical reinvestigation. Using this insight, we calculated the relative energy of FM and AFM orderings along [0.5 1 1], [0.5 0 0], [0 1 0], and [0 0 1] using noncollinear DFT calculations with spin-orbital coupling. In this work, we found that the [0.5 1 1] AFM structure is lower in energy than FM or AFM orderings along the low Miller index directions. We also investigated polarization of the magnetic moment along each lattice vector and found that polarization along the out-of-plane direction is the energetically preferred orientation for the AFM structures. Additionally, we found in all calculations that moments initially pointing along the in-plane lattice vectors significantly relax until they point along the coordinate between the two crystallographically distinct uranium sites with complex noncollinear magnetic configurations. The new [0.5 1 1] AFM magnetic structure provides an additional path forward toward understanding the electronic structure of α-U 3 O 8 and lends theoretical credibility to recent neutron scattering results.

36 MATERIALS SCIENCE↗
NASA NTRS1977

Comment on the relation between the nonadiabatic coupling and the complex intersection of potential energy curves

Simple relations are discussed that provide a correspondence between the complex intersection of two potential surfaces and the nonadiabatic coupling matrix element between those surfaces. These are key quantities in semiclassical and quantum-mechanical theories of collision-induced electronic transitions. Within the two-state approximation, the complex intersection is shown to be directly related to the location and magnitude of the peak in the nonadiabatic coupling. Two cases have been considered: (1) the avoided crossing between two potential surfaces, and (2) the spin-orbit interaction due to a 2P halogen atom. Comparisons are made between the results of the two-state model and the results of ab initio quantum chemical calculations.

Jaffe, R. L.↗
DOE OSTI2020

CI-MBPT line strengths and atomic probabilities for some transitions of neutral iodine

Iodine is a promising alternative to expensive xenon as a propellant for electric propulsion devices. Iodine optical spectroscopy is a valuable diagnostic tool for optimization of the iodine propellant. Recently, some measurements have been conducted with cells containing iodine plasma, and iodine atomic absorption at several wavelengths (911, 906, 206 and 1315 nm) was measured with a Ti:sapphire laser. Motivated by these experiments and future applications, here we have calculated line strengths and atomic probabilities for the transitions between different types of 5s 2 5p 5 , 5s 2 5p 4 6s, 5s 2 5p 4 6p and 5s 2 5p 4 5d states of atomic iodine, using configuration-interaction many-body perturbation theory. Since experimental transition data for atomic iodine are only available for a relatively small number of transitions, we also performed calculations for the bromine atom, to further validate our approach. We found good agreement between our theory and available experimental data for both elements in most cases. Therefore, we believe that our predicted line strengths and transition probabilities are quite reliable and will be useful for iodine spectroscopy.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Unconventional Hysteretic Transition in a Charge Density Wave

Hysteresis underlies a large number of phase transitions in solids, giving rise to exotic metastable states that are otherwise inaccessible. Here, we report an unconventional hysteretic transition in a quasi-2D material, EuTe 4 . By combining transport, photoemission, diffraction, and x-ray absorption measurements, we observe that the hysteresis loop has a temperature width of more than 400 K, setting a record among crystalline solids. The transition has an origin distinct from known mechanisms, lying entirely within the incommensurate charge density wave (CDW) phase of EuTe 4 with no change in the CDW modulation periodicity. We interpret the hysteresis as an unusual switching of the relative CDW phases in different layers, a phenomenon unique to quasi-2D compounds that is not present in either purely 2D or strongly coupled 3D systems. Furthermore, our findings challenge the established theories on metastable states in density wave systems, pushing the boundary of understanding hysteretic transitions in a broken-symmetry state.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Excited State Dynamics of a Conformationally Fluxional Copper Coordination Complex

The conversion of solar energy into chemical fuel represents a capstone goal of the 21st century and has the potential to supply terawatts of power in a globally distributed manner. However, the disparate time scales of photodriven charge separation (~fs) and steps in chemical reactions (~μs) represent an inherent bottleneck in solar-to-fuels technology. Here to address this discrepancy, we are developing earth-abundant coordination complexes that undergo light-induced conformational rearrangements such that charge separation (CS) is hastened, while charge recombination (CR) is slowed. To these ends, we report the preparation and characterization of a new series of conformationally fluxional copper coordination complexes that contain a twisted intramolecular charge transfer (TICT) fluorophore as part of their ligand scaffold. Structural and spectroscopic characterization of the Cu(I) and Cu(II) complexes formed with these ligands in their ground states establish oxidation state-dependent conformational dynamicity, while time-resolved emission and transient absorption spectroscopies define the photopysical parameters of photo-induced excited states. Building on initial reports with a related set of molecules, the improved ligand design presented here greatly simplifies the observed photophysics, effectively shutting down unwanted ligand-centered excited states previously observed. Finally, time-dependent density functional theory (TDDFT) analyses reveal an unusual metal-to-TICT electronic transition only reported once before, and though the formation of a CS state is not observed directly through experiments, TDDFT geometry optimizations in the excited states support the formation of transient Cu(II) CS species, lending credence to the potential success of our approach. These studies establish a clear model for the excited state dynamics at play in proof-of-concept systems and clarify key design parameters for future optimizations toward achieving long-lived CS via photoinduced conformational gating.

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

LDRD conclusion poster - Synthesizing Heterometallic Uranium Single Crystals to Understand the Influence of the Secondary Metals on Uranyl Axial Bond Strength

Understanding how transition metals influenced the chemistry of lanthanide and actinide (f-element) materials is critical for advancing separation technologies, materials design, and coordination chemistry. This project examined how incorporating first-row transition metals affected the structural and spectroscopic properties of f-element coordination polymers. In uranium(VI)-based systems synthesized with 2,6-pyridinedicarboxylic acid (PDC) ligands, single-crystal X-ray diffraction and Raman spectroscopy revealed that the presence of transition metals shortened the uranyl axial bond and induced a blue shift in its symmetric stretching vibration—evidence of increased bond strength. Electronic structure analysis, including Density of States (DOS) calculations using density functional theory (DFT), revealed altered orbital overlaps and highlighted the role of transition metal d-orbitals in modulating bonding. Raman modes were modeled using truncated structural fragments in collaboration with the University of Notre Dame, and although the predicted frequencies were lower than experimental values, they remained within expected ranges. In parallel, similar experiments with cerium (Ce) in the presence of cobalt (Co) and PDC demonstrated multi-step single-crystal-to-single-crystal transformations—behavior not observed in the uranium systems. Initial products included light yellow, orange, and polycrystalline materials. Single-crystal X-ray diffraction studies, conducted in collaboration with the Colorado School of Mines, identified the yellow phase as monometallic Ce(PDC)2(H2O)2·4H2O and the orange phase as heterometallic Ce2Co(PDC)4(H2O)6. After standing in solution for one week, both phases fully transformed into a dark yellow crystalline phase, [Ce3(PDC)5(H2O)8].6(H2O). Remarkably, this transformation was reversible—disturbing the equilibrium by removing some crystals caused reversion to the initial Ce(PDC)2(H2O)2·4H2O phase, highlighting dynamic behavior. All three structures were previously unreported. Solid-state UV-visible and Raman spectroscopy further distinguished these phases, revealing ligand-to-metal charge transfer involving Ce and characteristic d–d transitions from Co(II). The precise mechanism driving these transformations remained unclear; however, pH-dependent experiments confirmed that the transformation did not occur when the pH decreased. Overall, the project demonstrated that transition metals could be employed to tune bonding interactions, structural dimensionality, and optical properties in f-element materials, establishing new pathways for designing functional heterometallic systems. The work resulted in several novel structural discoveries and fostered productive collaborations with the University of Notre Dame and the Colorado School of Mines.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
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↗
DOE OSTI2023

Directional effects of antiferromagnetic ordering on the electronic structure in NdSb

The recent discovery of unconventional surface-state pairs, which give rise to Fermi arcs and spin textures, in antiferromagnetically ordered NdBi raised the interest in rare-earth monopnictides. Several scenarios of antiferromagnetic (AFM) order have been suggested to explain the origin of these states with some of them being consistent with the presence of nontrivial topologies. Here, in this paper, we use angle-resolved photoemission spectroscopy (ARPES) and density-functional-theory (DFT) calculations to investigate the electronic structure of NdSb. We found the presence of distinct domains that have different electronic structures at the surface. These domains correspond to different orientations of magnetic moments in the AFM state with respect to the surface. We demonstrated remarkable agreement between DFT calculations and ARPES that capture all essential changes in the band structure caused by the transition to a magnetically ordered state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Transition-state correlations for predicting thermochemistry of adsorbates and surface reactions

Estimating thermochemical properties from linear correlations may provide a pathway to circumvent expensive density functional theory (DFT) calculations for quantities such as pre-exponentials and temperature corrections to DFT energies. Here, in this work, we construct thermochemical scaling relations between C 1 –C 6 n-alkanes in the gas phase and adsorbed alkyl chains extending from several transition metal surfaces, and examine changes in the slope and fit between metals and adsorption sites. We subsequently add –OH, –NH 2 , C$=$O, and C$=$C functional groups to the C 1 –C 6 molecules and demonstrate strong linear correlations for thermochemistry across all species. We broaden the correlations to incorporate transition states of C 1 –C 6 n-alkane dehydrogenation reactions, where thermochemistry for computationally prohibitive transition-state calculations can be quickly assessed. Additionally, we rationalize the linearity of thermochemical correlations based on the composition of the homologous series and theoretical assessments. As an application of the correlations, we estimate pre-exponentials for elementary surface reactions of ethane and propane hydrogenolysis on Ru(0001), which is of relevance to plastic hydrogenolysis. Depending on kinetically important steps, entropic contributions may be necessary to include in certain reaction mechanisms; in contrasting examples, entropies are found to be relatively insignificant for ethane hydrogenolysis but pertinent for propane hydrogenolysis.

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

Electron transfer in nonpolar media

The Marcus theory of electron transfer views fluctuating orientations of permanent dipoles as the nuclear mode bringing the donor and acceptor into the tunneling resonance. Electronic polarization of the solvent is excluded as the fast mode adiabatically following the electronic density. This view, valid for solids, does not apply to molecular liquids where molecular translations (density fluctuations) modulate the induction interaction of the donor-acceptor complex with the solvent. This mechanism of promoting radiation-less electronic transitions is considered here in the framework of the perturbation liquid-state theory. The reorganization energy of electron transfer in nonpolar solvents is nonzero and reaches the values of 0.1–0.3 eV for typical molecular sizes and solvents used in applications. The reorganization energy scales quadratically with the molecular polarizability of the solvent and decays as the inverse fifth power with the size of the donor and acceptor. The combination of the entropic character of the density fluctuations, driven by re-packing of molecular cores, with the short range of induction solute–solvent interactions leads to the violation of the fluctuation–dissipation theorem for the variance of the donor-acceptor energy gap. An explicit, approximately hyperbolic, dependence of the reorganization energy on temperature is predicted. It leads to a non-Arrhenius kinetic law for the rate constant of electron transfer in nonpolar liquid solvents.

14 SOLAR ENERGY↗
NASA NTRS1990

Some theoretical aspects of boundary layer stability theory

Increased understanding in recent years of boundary layer transition has been made possible by the development of strongly nonlinear stability theories. After some twenty or so years when nonlinear stability theory was restricted to the application of the Stuart-Watson method (or less formal amplitude expansion procedures), there now exist strongly nonlinear theories which can describe processes which have an 0(1) effect on the basic state. These strongly nonlinear theories and their possible role in pushing theoretical understanding of transition ever further into the nonlinear regime are discussed.

Hall, Philip↗
DOE OSTI2022

Evidence for pressure induced unconventional quantum criticality in the coupled spin ladder antiferromagnet C 9 H 18 N 2 CuBr 4

Quantum phase transitions in quantum matter occur at zero temperature between distinct ground states by tuning a nonthermal control parameter. Often, they can be accurately described within the Landau theory of phase transitions, similarly to conventional thermal phase transitions. However, this picture can break down under certain circumstances. Here, we present a comprehensive study of the effect of hydrostatic pressure on the magnetic structure and spin dynamics of the spin-1/2 ladder compound C 9 H 18 N 2 CuBr 4 . Single-crystal heat capacity and neutron diffraction measurements reveal that the Néel-ordered phase breaks down beyond a critical pressure of Pc~1.0 GPa through a continuous quantum phase transition. Estimates of the critical exponents suggest that this transition may fall outside the traditional Landau paradigm. The inelastic neutron scattering spectra at 1.3 GPa are characterized by two well-separated gapped modes, including one continuum-like and another resolution-limited excitation in distinct scattering channels, which further indicates an exotic quantum-disordered phase above Pc.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Charge-induced atomic strain as a predictor of structural phase transformation in rare-earth intermetallics

We present a descriptor based on charge-induced atomic strain in crystalline lattices for predicting structural phase transformations in rare-earth intermetallic compounds containing lanthanides and transition metals. The charge-induced local atomic strain was obtained from structural optimization of experimentally known crystalline phases using state of the art density-functional theory methods. The predictive power of the descriptor was evaluated on 𝑅⁢𝐸 2 ⁢In (𝑅𝐸 = rare earth) compounds, a class known for diverse phase transformations. We show that incorporating quantum-mechanical effects—such as local charge distribution, bonding, symmetry, and electronic structure—enhances the robustness of the descriptor. To gain further insight, we analyzed phononic and electronic behavior in Y 2 ⁢In and demonstrated that experimental phase transformations are captured only when atomic strain effects are included. The descriptor was further used to predict structural phase changes in (Y⁢b 1–𝑥 ⁢E⁢r 𝑥 ) 2 ⁢In and G⁡d 2 ⁡(I⁢n 1–𝑥⁢ A⁢l 𝑥 ), with predictions confirmed by x-ray powder diffraction. Here, while the current study is focused on lanthanide-based intermetallics, the underlying principles of the descriptor suggest potential applicability to other closely related classes of rare-earth intermetallics.

Density functional theory↗
DOE OSTI2022

Electronic structure of strongly correlated systems: recent developments in multiconfiguration pair-density functional theory and multiconfiguration nonclassical-energy functional theory

Strong electron correlation plays an important role in transition-metal and heavy-metal chemistry, magnetic molecules, bond breaking, biradicals, excited states, and many functional materials, but it provides a significant challenge for modern electronic structure theory. The treatment of strongly correlated systems usually requires a multireference method to adequately describe spin densities and near-degeneracy correlation. However, quantitative computation of dynamic correlation with multireference wave functions is often difficult or impractical. Multiconfiguration pair-density functional theory (MC-PDFT) provides a way to blend multiconfiguration wave function theory and density functional theory to quantitatively treat both near-degeneracy correlation and dynamic correlation in strongly correlated systems; it is more affordable than multireference perturbation theory, multireference configuration interaction, or multireference coupled cluster theory and more accurate for many properties than Kohn–Sham density functional theory. This perspective article provides a brief introduction to strongly correlated systems and previously reviewed progress on MC-PDFT followed by a discussion of several recent developments and applications of MC-PDFT and related methods, including localized-active-space MC-PDFT, generalized active-space MC-PDFT, density-matrix-renormalization-group MC-PDFT, hybrid MC-PDFT, multistate MC-PDFT, spin–orbit coupling, analytic gradients, and dipole moments. We also review the more recently introduced multiconfiguration nonclassical-energy functional theory (MC-NEFT), which is like MC-PDFT but allows for other ingredients in the nonclassical-energy functional. We discuss two new kinds of MC-NEFT methods, namely multiconfiguration density coherence functional theory and machine-learned functionals.

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

Organismic materials for beyond von Neumann machines

The elementary basis of intelligence in organisms with a central nervous system includes neurons and synapses and their complex interconnections forming neural circuits. In non-neural organisms such as slime mold with gel-like media, viscosity modulation enables adaptation to changing environments. At a larger scale, collective intelligence emerges via social interactions and feedback in animal colonies. Learning and memory are therefore multi-scale features that evolve as a result of constant interactions with the environment. There is growing interest in emulating such features of intelligence in computing machines and autonomous systems. Materials that can respond to their environment in a manner similar to organisms (referred to as "organismic materials") therefore may be of interest as hardware components in artificial intelligence machines. In this brief review, we present a class of semiconductors called correlated oxides as candidates for learning machines. The term "correlated" refers to the fact that electrons in such lattices strongly interact and the ground state is not what is predicted by classical band theory. Such materials can undergo insulator-metal transitions at near ambient conditions under external stimuli such as thermal or electrical fields, strain, and chemical doping. Depending on the mechanism driving the transition, intermediate states can be metastable with different volatilities, and the time scales of phase change can be controlled over many orders of magnitude. The change in electronic properties can be sharp or gradual, leading to digital or analog behavior. These properties enable the realization of artificial neurons and synapses and emulate the associative and non-associative learning characteristics found in various organisms. We examine microscopic properties concerning electronic and structural transitions leading to collective behavior and theoretical treatments of the ground state and dynamical response, showcasing VO 2 as a model system. Next, we briefly review algorithms designed from the plasticity demonstrated by phase changing systems. Finally, we conclude the brief review with suggestions for future research toward realizing non-von Neumann machines.

42 ENGINEERING↗