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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Electrochemical Processes Breaking Strict Phase Electroneutrality in Microemulsions

Phase electroneutrality is a near-omnipresent assumption in electrochemical reactions. Even media such as biphasic oil-water interfaces and kinetically stable emulsions follow this “rule.” This implies all electron transfer reactions must be accompanied by ion transfer to maintain charge balance within a phase. However, due to the small domain size, electroneutrality is known to break down in the electric double layer adjacent to the electrode. Therefore, the appropriateness of the electroneutrality approximation for media with nanoscale domains, such as microemulsions, is questionable. Here, in this work, we show definitively, for the first time, that phase electroneutrality can be violated during an electron transfer reaction in microemulsions. Cyclic voltammograms show that electrochemical oxidation of rubrene is possible in microemulsions when sodium hydroxide is the only supporting electrolyte. Rubrene is a hydrophobic redox compound that is insoluble in water in neutral and radical cation forms, and hydroxide anions are too hydrophilic to transfer to the oil (toluene) phase. Contrary to observations made in emulsion systems, rubrene oxidation in microemulsions seemingly occurs by a mechanism where coupled ion transfer required for rigorous phase electroneutrality is negated. Our results demonstrate that electron transfer reactions within nanometer-sized domains are not subject to restrictions that govern systems with larger domains.

Barth, Brian A. [Univ. of Tennessee, Knoxville, TN↗
DOE OSTI2023

Relativistic resolution-of-the-identity with Cholesky integral decomposition

In this study, we present an efficient integral decomposition approach called the restricted-kinetic-balance resolution-of-the-identity (RKB-RI) algorithm, which utilizes a tunable RI method based on the Cholesky integral decomposition for in-core relativistic quantum chemistry calculations. The RKB-RI algorithm incorporates the restricted-kinetic-balance condition and offers a versatile framework for accurate computations. Notably, the Cholesky integral decomposition is employed not only to approximate symmetric large-component electron repulsion integrals but also those involving small-component basis functions. In addition to comprehensive error analysis, we investigate crucial conditions, such as the kinetic balance condition and variational stability, which underlie the applicability of Dirac relativistic electronic structure theory. Here we compare the computational cost of the RKB-RI approach with the full in-core method to assess its efficiency. To evaluate the accuracy and reliability of the RKB-RI method proposed in this work, we employ actinyl oxides as benchmark systems, leveraging their properties for validation purposes. This investigation provides valuable insights into the capabilities and performance of the RKB-RI algorithm and establishes its potential as a powerful tool in the field of relativistic quantum chemistry.

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

Electronic descriptors for dislocation deformation behavior and intrinsic ductility in bcc high-entropy alloys

Controlling the balance between strength and damage tolerance in high-entropy alloys (HEAs) is central to their application as structural materials. Materials discovery efforts for HEAs are therefore impeded by an incomplete understanding of the chemical factors governing this balance. Through first-principles calculations, this study explores factors governing intrinsic ductility of a crucial subset of HEAs—those with a body-centered cubic (bcc) crystal structure. Analyses of three sets of bcc HEAs comprising nine different compositions reveal that alloy chemistry profoundly influences screw dislocation core structure, dislocation vibrational properties, and intrinsic ductility parameters derived from unstable stacking fault and surface energies. Key features in the electronic structure are identified that correlate with these properties: the fraction of occupied bonding states and bimodality of the d-orbital density of states. The findings enhance the fundamental understanding of the origins of intrinsic ductility and establish an electronic structure–based framework for computationally accelerated materials discovery and design.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Resolving Electron Injection from Singlet Fission-Borne Triplets into Mesoporous Transparent Conducting Oxides

Photoinduced electron transfer from a molecular chromophore into mesoporous metal oxide substrates occurs efficiently from both singlet and triplet excited states for traditional metal-to-ligand charge transfer (MLCT) dyes. All organic molecules that undergo singlet fission (SF), the process of generating two triplet excitons with photoexcitation of one singlet exciton, offers a promising method of generating two charges per one absorbed photon. However, the singlet-triplet energy balance required to drive SF often places the driving force for triplet electron injection into metal oxides too low. As such, the dynamics of singlet vs. triplet electron transfer for SF in dye-sensitized solar cell configurations has not been elucidated. Here, we use applied bias transient absorption spectroscopy to modulate the driving force for triplet electron transfer from an anthradithiophene-based SF chromophore (ADT-COOH) adsorbed to mesoporous indium tin oxide (nanoITO).

CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SU↗
DOE OSTI2023

The anisotropic nature of singlet fission in single crystalline organic semiconductors

The escalating global energy predicament implores for a revolutionary resolution—one that converts sunlight into electricity—holding the key to supreme conversion efficiency. This comprehensive review embarks on the exploration of the principle of generating multiple excitons per absorbed photon, a captivating concept that possesses the potential to redefine the fundamental confines of conversion efficiency, albeit its application remains limited in photovoltaic devices. At the nucleus of this phenomenon are two principal processes: multiple exciton generation (MEG) within quantum-confined environments, and singlet fission (SF) inside molecular crystals. The process of SF, characterized by the cleavage of a single photogenerated singlet exciton into two triplet excitons, holds promise to potentially amplify photon-to-electron conversion efficiency twofold, thereby laying the groundwork to challenge the detailed balance limit of solar cell efficiency. Our discourse primarily dissects the complex nature of SF in crystalline organic semiconductors, laying special emphasis on the anisotropic behavior of SF and the diffusion of the subsequent triplet excitons in single-crystalline polyacene organic semiconductors. We initiate this journey of discovery by elucidating the principles of MEG and SF, tracing their historical genesis, and scrutinizing the anisotropy of SF and the impact of quantum decoherence within the purview of functional mode electron transfer theory. We present an overview of prominent techniques deployed in investigating anisotropic SF in organic semiconductors, including femtosecond transient absorption microscopy and imaging as well as stimulated Raman scattering microscopies, and highlight recent breakthroughs linked with the anisotropic dimensions of Davydov splitting, Herzberg–Teller effects, SF, and triplet transport operations in single-crystalline polyacenes. Through this comprehensive analysis, our objective is to interweave the fundamental principles of anisotropic SF and triplet transport with the current frontiers of scientific discovery, providing inspiration and facilitating future ventures to harness the anisotropic attributes of organic semiconductor crystals in the design of pioneering photovoltaic and photonic devices.

Chemistry↗
DOE OSTI2023

Electronic noise of a single skyrmion

To enable the practical use of skyrmion-based devices, it is essential to achieve a balance between energy efficiency and thermal stability while also ensuring reliable electrical detection against noise. Understanding how a skyrmion interacts with material disorder and external perturbations is thus essential. Here, we investigate the electronic noise of a single skyrmion under the influence of thermal fluctuations and spin currents in a magnetic thin film. We detect the thermally induced noise with a 1/ƒ $\gamma$ signature in the strong pinning regime but a random telegraph noise in the intermediate pinning regime. Both the thermally dominated and current-induced telegraphlike signals are detected in the weak pinning regime. Our results provide a comprehensive electronic noise picture of a single skyrmion, demonstrating the potential of noise fluctuation as a valuable tool for characterizing the pinning condition of a skyrmion. In conclusion, these insights could also aid in the development of low-noise and reliable skyrmion-based devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Guest Editorial Special Issue on Emerging Topics of Power Electronics Interfaced Battery Energy Storage System

No doubt, battery energy storage systems have been the enabling solution to balance generation and consumption of power systems with high-penetration renewable energy resources, long-range electric vehicles, and various smart devices. Upon the battery has been manufactured, the rest of implementation issues become how to interface battery and related systems, how to regulate the charging/discharging power, and how to keep battery energy storage systems (BESSs) safe, reliable, and long-term service. In this editorial, we discuss how power electronic converters and associated control and optimization, which can maximize the value of BESSs, are devoted to provide cost-effective, efficient, and even revolutionary technologies.

25 ENERGY STORAGE↗
DOE OSTI2021

Excited States of Crystalline Point Defects with Multireference Density Matrix Embedding Theory

Accurate and affordable methods to characterize the electronic structure of solids are important for targeted materials design. Embedding-based methods provide an appealing balance in the trade-off between cost and accuracy-particularly when studying localized phenomena. Here, we use the density matrix embedding theory (DMET) algorithm to study the electronic excitations in solid-state defects with a restricted open-shell Hartree-Fock (ROHF) bath and multireference impurity solvers, specifically, complete active space self-consistent field (CASSCF) and n-electron valence state second-order perturbation theory (NEVPT2). In this work, we apply the method to investigate the electronic excitations in an oxygen vacancy (OV) on a MgO(100) surface and find absolute deviations within 0.05 eV between DMET using the CASSCF/NEVPT2 solver, denoted as CAS-DMET/NEVPT2-DMET, and the nonembedded CASSCF/NEVPT2 approach. Next, we establish the practicality of DMET by extending it to larger supercells for the OV defect and a neutral silicon vacancy in diamond where the use of nonembedded CASSCF/NEVPT2 is extremely expensive.

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

Chemical Bonding and the Role of Node-Induced Electron Confinement

The chemical bond is the cornerstone of chemistry, providing a conceptual framework to understand and predict the behavior of molecules in complex systems. However, the fundamental origin of chemical bonding remains controversial and has been responsible for fierce debate over the past century. Here, in this study, we present a unified theory of bonding, using a separation of electron delocalization effects from orbital relaxation to identify three mechanisms [node-induced confinement (typically associated with Pauli repulsion, though more general), orbital contraction, and polarization] that each modulate kinetic energy during bond formation. Through analysis of a series of archetypal bonds, we show that an exquisite balance of energy-lowering delocalizing and localizing effects are dictated simply by atomic electron configurations, nodal structure, and electronegativities. The utility of this unified bonding theory is demonstrated by its application to explain observed trends in bond strengths throughout the periodic table, including main group and transition metal elements.

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

Site-Differentiated Iron–Sulfur Cluster Ligation Affects Flavin-Based Electron Bifurcation Activity

Electron bifurcation is an elegant mechanism of biological energy conversion that effectively couples three different physiologically relevant substrates. As such, enzymes that perform this function often play critical roles in modulating cellular redox metabolism. One such enzyme is NADH-dependent reduced-ferredoxin: NADP+ oxidoreductase (NfnSL), which couples the thermodynamically favorable reduction of NAD+ to drive the unfavorable reduction of ferredoxin from NADPH. The interaction of NfnSL with its substrates is constrained to strict stoichiometric conditions, which ensures minimal energy losses from non-productive intramolecular electron transfer reactions. However, the determinants for this are not well understood. One curious feature of NfnSL is that both initial acceptors of bifurcated electrons are unique iron–sulfur (FeS) clusters containing one non-cysteinyl ligand each. The biochemical impact and mechanistic roles of site-differentiated FeS ligands are enigmatic, despite their incidence in many redox active enzymes. Herein, we describe the biochemical study of wild-type NfnSL and a variant in which one of the site-differentiated ligands has been replaced with a cysteine. Results of dye-based steady-state kinetics experiments, substrate-binding measurements, biochemical activity assays, and assessments of electron distribution across the enzyme indicate that this site-differentiated ligand in NfnSL plays a role in maintaining fidelity of the coordinated reactions performed by the two electron transfer pathways. Given the commonality of these cofactors, our findings have broad implications beyond electron bifurcation and mechanistic biochemistry and may inform on means of modulating the redox balance of the cell for targeted metabolic engineering approaches.

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

Impact of environmental oxygen on nanoparticle formation and agglomeration in aluminum laser ablation plumes

Here, the role of ambient oxygen gas (O 2 ) on molecular and nanoparticle formation and agglomeration was studied in laser ablation plumes. As a lab-scale surrogate to a high explosion detonation event, nanosecond laser ablation of an aluminum alloy (AA6061) target was performed in atmospheric pressure conditions. Optical emission spectroscopy and two mass spectrometry techniques were used to monitor the early to late stages of plasma generation to track the evolution of atoms, molecules, clusters, nanoparticles, and agglomerates. The experiments were performed under atmospheric pressure air, atmospheric pressure nitrogen, and 20% and 5% O 2 (balance N 2 ), the latter specifically with in situ mass spectrometry. Electron microscopy was performed ex situ to identify crystal structure and elemental distributions in individual nanoparticles. We find that the presence of ≈20% O 2 leads to strong AlO emission, whereas in a flowing N 2 environment (with trace O 2 ), AlN and strong, unreacted Al emissions are present. In situ mass spectrometry reveals that as O 2 availability increases, Al oxide cluster size increases. Nanoparticle agglomerates formed in air are found to be larger than those formed under N 2 gas. High-resolution transmission electron microscopy demonstrates that Al 2 O 3 and AlN nanoparticle agglomerates are formed in both environments; indicating that the presence of trace O 2 can lead to Al 2 O 3 nanoparticle formation. The present results highlight that the availability of O 2 in the ambient gas significantly impacts spectral signatures, cluster size, and nanoparticle agglomeration behavior. These results are relevant to understanding debris formation in an explosion event, and interpreting data from forensic investigations.

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

Role of the edge stochastic layer in density pump-out by resonant magnetic perturbations

The role of the edge stochastic layer on particle transport is addressed in DIII-D plasmas with applied resonant magnetic perturbations (RMPs) causing density pump-out (a term used to denote the density reduction at the top of the pedestal due to the applied RMPs). Using an analytical model that adds the stochastic parallel transport of electrons (Harvey et al 1981 Phys. Rev. Lett. 47 102) to the fluid equations, the ambipolar radial electric field and particle flux are calculated simultaneously. In this model the nonambipolar electron particle flux, driven by the stochastic magnetic field, is predominantly balanced by the nonambipolar perpendicular ion flux, driven by toroidal viscosity, across a narrow stochastic layer of order two percent of the plasma radius (0.98 < ψn < 1). The model reproduces the level of density pump-out and its dependence on RMP amplitude near the separatrix for three plasma discharges for which the pedestal foot is at medium to high collisionality $(2\leqslant {\nu }_{\text{sep}}^{\ast }\leqslant 30)$. In this work, the experimentally observed and numerically tested inverse density dependence of density pump-out (Hu et al 2020 Nucl. Fusion 60 076001) is accurately captured by the model: an increase in collisionality with density in the pedestal foot results in a decrease in stochastic diffusivity, and hence a decrease in the level of pump-out.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Effects of electron viscosity on resonant layer responses to non-axisymmetric magnetic perturbations

The resonant field penetration to magnetic islands is the central MHD mechanism of non-axisymmetric plasma responses in a tokamak such as disruptive locking or favorable ELM stabilization. The resonant field penetration can be induced by any non-ideal processes as manifested in the delicate balance under the generalized Ohm's law. Here, we show that the viscous effects by electrons are not ignorable in the field penetration unlike previous presumption, even if the electron viscosity is as small as the square root of its mass compared to the ions. It is clear that its effects become only bigger if the electron viscosity becomes anomalously large. The work strictly follows the three-field model in the linear regime targeting the prediction of the onset of the field penetration and successfully extending it with electron viscosity and identifying new regimes. The results also indicate that the error field thresholds become more strongly dependent on plasma density than ones predicted in the linear regimes without the electron viscosity, which is consistent with experimental observations and thus a significant implication.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Isotope effects on energy transport in the core of ASDEX-Upgrade tokamak plasmas: Turbulence measurements and model validation

Design and operation of future tokamak fusion reactors using a deuterium–tritium 50:50 mix requires a solid understanding of how energy confinement properties change with ion mass. This study looks at how turbulence and energy transport change in L-mode plasmas in the ASDEX Upgrade tokamak when changing ion species between hydrogen and deuterium. For this purpose, both experimental turbulence measurements and modeling are employed. Local measurements of ion-scale (with wavevector of fluctuations perpendicular to the B-field k⊥< 2 cm−1, k⊥ρs< 0.2, where ρs is the ion sound Larmor radius using the deuterium ion mass) electron temperature fluctuations have been performed in the outer core (normalized toroidal flux ρTor=0.65−0.8) using a multi-channel correlation electron cyclotron emission diagnostic. Lower root mean square perpendicular fluctuation amplitudes and radial correlation lengths have been measured in hydrogen vs deuterium. Measurements of the cross-phase angle between a normal-incidence reflectometer and an ECE signal were made to infer the cross-phase angle between density and temperature fluctuations. The magnitude of the cross-phase angle was found larger (more out-of-phase) in hydrogen than in deuterium. TRANSP power balance simulations show a larger ion heat flux in hydrogen where the electron-ion heat exchange term is found to play an important role. These experimental observations were used as the basis of a validation study of both quasilinear gyrofluid trapped gyro-Landau fluid-SAT2 and nonlinear gyrokinetic GENE codes. Linear solvers indicate that, at long wavelengths (k⊥ρs<1), energy transport in the deuterium discharge is dominated by a mixed ion-temperature-gradient (ITG) and trapped-electron mode turbulence while in hydrogen transport is exclusively and more strongly driven by ITG turbulence. The Ricci validation metric has been used to quantify the agreement between experiments and simulations taking into account both experimental and simulation uncertainties as well as four different observables across different levels of the primacy hierarchy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Many-Body Benchmark of Electronic Charge and Spin Densities for Li 1–x NiO 2

Accurate benchmarks are particularly important for highly correlated oxides as mean-field approximations often fail to describe the subtle balance of charge transfer and magnetism in these materials with an accuracy comparable to experimental needs. Here we present accurate diffusion Monte Carlo (DMC) results of the electronic charge and spin densities for the tunable highly correlated oxide Li 1–x NiO 2 for x = 0, 1/2, and 1. To enable quantitative comparisons, we introduce a robust density-partitioning scheme, extending Voronoi analysis to assign atomic charges from spatially noisy DMC densities. We then benchmark common approximations used in density functional theory (DFT). Comparison against DMC shows that r 2 SCAN delivers the most balanced performance across charge, spin, and radial density descriptors, nearly reproducing DMC results for LiNiO 2 and apical Ni sites in Li 0.5 NiO 2 . Hybrid functionals (PBE0, SCAN0) perform unexpectedly poorly, and PBE + U + V yields inconsistent trends between charge and spin densities. Therefore, the r 2 SCAN functional minimizes errors relative to DMC while capturing the variable valence of the Ni ion and also retaining the computational efficiency of DFT for large-scale simulations of the tunable structural and electronic phases of Li1−xNiO2. Our study highlights the importance of accurate benchmarking of the fundamental quantities involved in DFT to select appropriate DFT approximations in order to advance the predictive modeling of charge-transfer-driven phenomena in correlated electron systems.

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

Classical Preoptimization Approach for ADAPT-VQE: Maximizing the Potential of High-Performance Computing Resources to Improve Quantum Simulation of Chemical Applications

The ADAPT-VQE algorithm is a promising method for generating a compact ansatz based on derivatives of the underlying cost function, and it yields accurate predictions of electronic energies for molecules. In this work, we report the implementation and performance of ADAPT-VQE with our recently developed sparse wave function circuit solver (SWCS) in terms of accuracy and efficiency for molecular systems with up to 52 spin orbitals. The SWCS can be tuned to balance computational cost and accuracy, which extends the application of ADAPT-VQE for molecular electronic structure calculations to larger basis sets and a larger number of qubits. Using this tunable feature of the SWCS, we propose an alternative optimization procedure for ADAPT-VQE to reduce the computational cost of the optimization. Furthermore, by preoptimizing a quantum simulation with a parametrized ansatz generated with ADAPT-VQE/SWCS, we aim to utilize the power of classical high-performance computing in order to minimize the work required on noisy intermediate-scale quantum hardware, which offers a promising path toward demonstrating quantum advantage for chemical applications.

ADAPT-VQE↗
DOE OSTI2021

New understanding of inter-ELM pedestal turbulence, transport, and gradient behavior in the DIII-D tokamak

New observations of pedestal localized turbulence in the inter-ELM period of H-mode plasmas in DIII-D show that ion temperature gradient mode scale (ITG-scale) density fluctuation (ñ) increases immediately after each ELM crash and is quickly suppressed during the increase in local E × B shear. This excitation and subsequent suppression of ITG-scale ñ can explain the previously reported anomalous ion heat flux, Qi during the ELM (Viezzer et al 2017 Nucl. Fusion 57 022020). Shorter wavelength trapped electron mode scale (TEM-scale) ñ starts to increase at a critical pedestal temperature gradient (∇Te,ped) and saturates as local E × B shear, ${T}_{\mathrm{i}}^{\mathrm{C}\mathrm{6}+}/{T}_{\mathrm{e}}$ ratio, and ∇Te,ped saturate. This TEM-scale ñ, which has the potential to cause electron (and also ion) heat transport, is consistent with driving an anomalous electron heat flux Qe, where Qe is estimated between ELMs using experimental profiles and power balance. Both ITG- and TEM-scale ñ amplitude variations with background Ti/Te and ∇ne,ped are found to be consistent with theoretical predictions of these measured density fluctuations being ITG and TEM instabilities respectively. Furthermore, these new and unique observations on the nature of turbulence and their potential contributions to electron and ion heat fluxes at different ELM periods (i.e. collapse, recovery, and saturation phases of pedestal gradients) can significantly test and improve our pedestal predictive capabilities for ITER and other future fusion devices.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗