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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Minimizing Optimal Transport for Functions with Fixed-Size Nodal Sets

Consider the class of zero-mean functions with fixed L ∞ and L 1 norms and exactly N ϵ N nodal points. Which functions f minimize W p (f + ,f – ), the Wasserstein distance between the measures whose densities are the positive and negative parts? We provide a complete solution to this minimization problem on the line and the circle, which provides sharp constants for previously proven “uncertainty principle”-type inequalities, i.e., lower bounds on N • W p (f + ,f – ). We further show that, while such inequalities hold in many metric measure spaces, they are no longer sharp when the non-branching assumption is violated; indeed, for metric star-graphs, the optimal lower bound on W p (f + ,f – ) is not inversely proportional to the size of the nodal set, N. Here, based on similar reductions, we make connections between the analogous problem of minimizing W p (f + ,f – ) for f defined on Ω C R d with an equivalent optimal domain partition problem.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Natural Charge-Transfer Analysis: Eliminating Spurious Charge-Transfer States in Time-Dependent Density Functional Theory via Diabatization, with Application to Projection-Based Embedding

For many types of vertical excitation energies, linear-response time-dependent density functional theory (LR-TDDFT) offers a useful degree of accuracy combined with unrivaled computational efficiency, although charge-transfer excitation energies are often systematically and dramatically underestimated, especially for large systems and those that contain explicit solvent. As a result, low energy electronic spectra of solution-phase chromophores often contain tens to hundreds of spurious charge-transfer states, making LR-TDDFT needlessly expensive in bulk solution. More nefariously, intensity borrowing by the low-energy charge-transfer states can affect intensities of the valence excitations even if those excitation energies are accurate. At higher excitation energies, it is difficult to distinguish spurious CT states from genuine charge-transfer-to-solvent (CTTS) excitations. In this work, we introduce an automated diabatization scheme that enables fast and effective screening of the CTTS acceptor space in bulk solution. Our procedure introduces the concept of “natural charge-transfer orbitals”, which provide a means to isolate characteristic pairs of orbitals that are most likely to participate in a CTTS excitation. The projection of these orbitals onto solvent-centered virtual orbitals provides a criterion for defining the most important solvent molecules in a given excitation. We apply this method to analyze an ab initio molecular dynamics (MD) trajectory of I-(aq) and report the lowest-energy CTTS band in the absorption spectrum. Our results are in excellent agreement with experimental measurements for bulk I-(aq), and only one-third of the water molecules in the I-(H2O)96 simulation cell need to be described with LR-TDDFT in order to obtain excitation energies that are converged to < 0.1 eV. The tools introduced herein will improve the accuracy, efficiency, and usability of LR-TDDFT in solution-phase environments

Carter-Fenk, Kevin D.↗
DOE OSTI2021

Uncertainty Quantification and Error Propagation in the Enthalpy and Entropy of Surface Reactions Arising from a Single DFT Functional

Accounting for parametric uncertainty in models is essential for quantifying the models’ predictive ability. Recently, approaches have been introduced to estimate parametric uncertainty in kinetic models while accounting for correlations among energy parameters. However, correlations have been estimated indirectly and correlations in entropies have not been accounted for. For surface-catalyzed microkinetic models of >C2 (more than two carbon-containing) molecules, which consist of thousands of reaction steps and intermediate surface species, first-principles density functional theory (DFT) is costly, and thus, estimation of thermochemistry and reaction barriers requires surrogate methods of DFT, such as group additivity and Brønsted–Evans–Polanyi relationships, respectively. For such parametrization, model uncertainty is unclear. This work develops a framework to overcome these gaps using group additivity and a single DFT functional. We estimate correlations in parameters of kinetic models and quantify uncertainty for thermochemistry, reaction barriers, reaction paths, and ultimately reaction rates, accounting also for the contribution of entropic uncertainty. Furthermore, the approach is illustrated on propane combustion and ethane oxidative dehydrogenation reactions.

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

Impact of Confinement and Zwitterionic Ligand Chemistry on Ion–Ion Selectivity of Functionalized Nanopores

Membranes incorporating zwitterionic chemistries have recently emerged as promising candidates for facilitating challenging ion–ion separations. Transport of ions in such membranes predominantly occurs in hydrated nanopores lined with zwitterionic monomers. Here, to shed light on the physics of ion–ion selectivity underlying such materials, we conducted molecular dynamics simulations of sodium halide transport in model nanopores grafted with sulfobetaine methacrylate molecules. Our results reveal that in both functionalized and unfunctionalized nanopores smaller ions prefer to reside near the pore center, while the larger ions tend to reside near the pore walls. An enhancement in the selective transport of larger anions is observed within the unfunctionalized nanopores relative to that in salt-in-water solutions. Upon functionalization of the nanopores with zwitterions (ZIs), the disparities in the anionic distribution profiles within the pores coupled with differences in the anion-ZI interactions result in a slowdown of larger anions relative to smaller anions. Increasing the ZI grafting density exacerbates these effects, further promoting the selective transport of smaller anions. Our results suggest that selectivity toward large anions can be realized by using nanoporous membranes with ZI content that is high enough to facilitate ion/water partitioning into the pores while preserving the characteristic tendency of the unfunctionalized pores to facilitate faster transport of the larger anions. On the other hand, selectivity toward smaller anions can be achieved by targeting ZI content within the pores that is high enough to significantly slow down the transport of large anions but not high enough to hinder the partitioning of ions/water molecules into the pore due to steric effects.

anions↗
DOE OSTI2022

Cation–Ligand Interactions Dictate Salt Partitioning and Diffusivity in Ligand-Functionalized Polymer Membranes

Membranes are an attractive alternative to current thermal separations due to their scalability and energy efficiency in desalinating water. Unfortunately, many of the conventional membrane materials available today are unable to differentiate between ionic solutes, especially alkali cations, compromising their use in ion–ion separations. Inspired by the ion-specific interactions exhibited by biological ion channels, recent research efforts have focused on synthesizing and characterizing new polymeric materials that incorporate ligands into polymer networks to bias solubility and/or diffusivity of one cationic species over another. Despite these efforts, little is known about the influence of incorporating ligands into polymer membranes on solubility and diffusivity of the complexing species. In this study, we first build a qualitative model of salt partitioning, diffusivity, and permeability in generic cation-complexing ligand-functionalized polymer membranes. Next, to validate our model and hypotheses, we perform atomistic molecular dynamics simulations of a 12-crown-4-functionalized membrane in the presence of alkali halide salts at low concentration. Generally, cation complexation enhances cation solubility but decreases diffusivity. Interestingly, the reduction in diffusivity is predicted to be larger than the enhancement in solubility for materials which operate by the mechanisms proposed in our physical picture, ultimately resulting in a reduction in the permeability of the selectively complexing ion.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Dual Functional Ni3S2@Ni Core-Shell Nanoparticles Decorating Nanoporous Carbon as Cathode Scaffolds for Lithium-Sulfur Battery with Lean Electrolytes

Lithium-sulfur batteries are very promising for next-generation energy storage. However, most studies use flooded electrolytes to achieve a high specific capacity at the expense of lowering the specific energy. Understanding lithium-sulfur battery performance with lean electrolytes is highly desirable. Herein, a modified Pechini method is developed to synthesize a nanoporous carbon host decorated with Ni3S2@Ni particles. Such a cathode delivers enhanced specific capacities with extended cycling life in lean electrolytes, due to the dual functions of the Ni3S2 shell, which can both facilitate reaction kinetics and promote electrolyte wetting. This work highlights a strategy to rationally design cathodes for highenergy lithium-sulfur batteries.

Zhang, Yulun↗
DOE OSTI2020

Nanoconfinement of Molecular Magnesium Borohydride Captured in a Bipyridine-Functionalized Metal-Organic Framework

The lower limit of metal hydride nanoconfinement is demonstrated through the coordination of a molecular hydride species to binding sites inside the pores of a metal-organic framework (MOF). Magnesium borohydride, which has a high hydrogen capacity, is incorporated into the pores of UiO-67bpy (Zr6O4(OH)4(bpydc)6 with bpydc2- = 2,2'-bipyridine-5,5'- dicarboxylate) by solvent impregnation. The MOF retained its long-range order, and transmission electron microscopy and elemental mapping confirmed the retention of the crystal morphology and revealed a homogeneous distribution of the hydride within the MOF host. Notably, the B-, N-, and Mg-edge XAS data confirm the coordination of Mg(II) to the N atoms of the chelating bipyridine groups. In situ 11B MAS NMR studies helped elucidate the reaction mechanism and revealed that complete hydrogen release from Mg(BH4)2 occurs as low as 200 °C. Sieverts and thermogravimetric measurements indicate an increase in the rate of hydrogen release, with the onset of hydrogen desorption as low as 120 °C, which is approximately 150 °C lower than that of the bulk material. Furthermore, density functional theory calculations support the improved dehydrogenation properties and confirm the drastically lower activation energy for B-H bond dissociation.

Nanoconfinement, Metal Hydrides, Metal-Organic Fra↗
DOE OSTI2020

Rethinking the magnetic properties of lepidocrocite: A density functional theory and cluster expansion study

The iron oxyhydroxide lepidocrocite (g-FeOOH) is an abundant mineral critical to a number of chemical and technological applications. Of particular interest is the ground state and nite temperature magnetic order, and the subsequent impact this has upon crystal properties. The magnetic properties, investigated in this work are governed primarily through superexchange interactions, and have been calculated using density functional theory and cluster expansion methods. Quantication of these exchange terms has facilitated the determination of the ground state magneto-crystalline structure and subsequent calculation of its lattice constants, elastic moduli, cohesive enthalpy, and electronic density of states. Further, using a collinear magnetic conguration model, the magnetic heat capacity versus temperature has been studied and the Neel temperature obtained.

Pope, Daniel J.↗
DOE OSTI2022

Fresnel zone plate point spread function approximation for zeroth order mitigation in millimetric field of view x-ray imaging

High spatial and temporal resolution x-ray radiography images are required at the National Ignition Facility (NIF) for high-energy density experiments. One technique that is in development to achieve the required resolution uses Fresnel zone plate (FZP) optics to image an object that is backlit by an x-ray source. The multiple FZP diffraction orders do not focus on the same plane, which increases the background and reduces the contrast. Understanding the point spread function of the different diffraction orders will allow the prediction of the expected background using simulations. We find that the two-dimensional point spread function of the FZP can be approximated by the addition of a sharp Gaussian with a disk. This allowed for the estimation of the background in NIF experimental images of Rayleigh–Taylor spikes and their interpretation. An alternative design of FZP is discussed to allow the inclusion of a zeroth order blocker to reduce the background.

Do, A. (ORCID:0000000174372147)↗
DOE OSTI2020

Impacts of nitrogen addition on switchgrass root-associated diazotrophic community structure and function

ABSTRACT Cellulosic bioenergy crops, like switchgrass (Panicum virgatum), have potential for growth on lands unsuitable for food production coupled with potential for climate mitigation. Sustainability of these systems lies in identifying conditions that promote high biomass yields on marginal lands under low-input agricultural practices. Associative nitrogen fixation (ANF) is a potentially important nitrogen (N) source for these crops, yet ANF contributions to plant N, especially under fertilizer N addition are unclear. In this study, we assess structure (nifH) and function (ANF) of switchgrass root-associated diazotrophic communities to long-term and short-term N additions using soil from three marginal land sites. ANF rates were variable and often unexpectedly high, sometimes 10× greater than reported in the literature, and did not respond in repeatable ways to long-term or short-term N. We found few impacts of N addition on root-associated diazotrophic community structure or membership. Instead, we found a very consistent root-associated diazotrophic community even though switchgrass seeds were germinated in soil from field sites with distinct diazotrophic communities. Ultimately, this work demonstrates that root-associated diazotrophic communities have the potential to contribute to switchgrass N demands, independent of N addition, and this may be driven by selection of the diazotrophic community by switchgrass roots.

Microbiology↗
DOE OSTI2021

Bulk Diffusion of Cl through O Vacancies in α-Cr 2 O 3 : A Density Functional Theory Study

Many metals form passive oxides which are broken or weakened by anionic-induced degradation leading to material failure and anionic diffusion is an important step of this degradation process. The diffusion of anionic species through oxides involves a combination of diffusion along grain boundaries, cracks, and channels, as well as bulk diffusion via point defects which is the focus of this study. Using density functional theory, we study bulk diffusion of Cl through O vacancies in α -Cr 2 O 3 as a model system for passive metal oxides. Little is known about Cl diffusion and bonding characteristics, so we benchmark our work through comparison to numerous studies on O diffusion in α -Cr 2 O 3 to analyze similarities and differences between the O and Cl diffusion in the passivation and degradation process of α -Cr 2 O 3 respectively. Unlike O diffusion, the lowest diffusion barrier for Cl is cross-plane diffusion between two (0001) planes through a vacant cation site but the much shorter in-plane diffusion path within the same coordination polyhedron has 35% higher barrier. This work provides the basis for considering the contributions of Cl bulk-diffusion in the overall diffusion kinetics of Cl through α -Cr 2 O 3 .

Oware Sarfo, Kofi↗
DOE OSTI2024

Topography and Functional Traits Control the Distribution of Key Shrub Plant Functional Types in Low-Arctic Tundra: Supporting Data

High-resolution classification maps derived from occupied aerial systems (UASs). The UAS data were collected in August 2021 using a Skydio 2+ drone equipped with a 4K resolution red-green-blue (RGB) camera (2024 Skydio Inc) and a 3DR SOLO Quadcopter carried a Parrot Sequoia+ Multispectral Sensor (2023 Parrot Drone SAS). This package includes vegetation classification maps at four locations around Next Generation Ecosystem Experiment Arctic (NGEE Arctic) Council watershed study site on the Seward Peninsula, Alaska. The classification maps were generated using a combination of RGB and canopy height information. The map data and metadata are provided as ENVI image (.dat) and text (.txt, *hdr) formats. Additional map quicklooks are provided as GIS *.kml files. These datasets are provided in support of Yang et al., (In review), “Topography and Functional Traits Control the Distribution of Key Shrub Plant Functional Types in Low-Arctic Tundra”.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a 15-year research effort (2012-2027) to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

SILVERRUSH. XIV. Ly α Luminosity Functions and Angular Correlation Functions from 20,000 Ly α Emitters at z ∼ 2.2–7.3 from up to 24 deg 2 HSC-SSP and CHORUS Surveys: Linking the Postreionization Epoch to the Heart of Reionization

Abstract We present luminosity functions (LFs) and angular correlation functions (ACFs) derived from 18,960 Ly α emitters (LAEs) at z = 2.2−7.3 over a wide survey area of ≲24 deg 2 that are identified in the narrowband data of the HSC-SSP and CHORUS surveys. Confirming the large sample with 241 spectroscopically identified LAEs, we determine Ly α LFs and ACFs in the brighter luminosity range down to 0.5 L ⋆ , and confirm that our measurements are consistent with previous studies but offer significantly reduced statistical uncertainties. The improved precision of our ACFs allows us to clearly detect one-halo terms at some redshifts, and provides large-scale bias measurements that indicate host halo masses of ∼10 11 M ⊙ over z ≃ 2−7. By comparing our Ly α LF (ACF) measurements with reionization models, we estimate the neutral hydrogen fractions in the intergalactic medium to be x H i < 0.05 (= 0.06 − 0.03 + 0.12 ) at z = 5.7 and x H i = 0.1 5 − 0.08 + 0.10 ( 0.21 − 0.14 + 0.19 ), 0.1 8 − 0.12 + 0.14 , and 0.7 5 − 0.13 + 0.09 at z = 6.6, 7.0, and 7.3, respectively. Our findings suggest that the neutral hydrogen fraction remains relatively low, x H i ≲ 0.2, at z = 5−7, but increases sharply at z > 7, reaching x H i ∼ 0.9 by z ≃ 8−9, as indicated by recent JWST studies. The combination of our results from LAE observations with recent JWST observations suggests that the major epoch of reionization occurred at z ∼ 7−8, likely driven by the emergence of massive sources emitting significant ionizing photons.

Umeda, Hiroya (ORCID:0009000801675129)↗
DOE OSTI2021

An SYK-inspired model with density–density interactions: Spectral & wave function statistics, Green’s function and phase diagram

The Sachdev–Ye–Kitaev (SYK) model is a rare example of a strongly-interacting system that is analytically tractable. Tractability arises because the model is largely structureless by design and therefore artificial: while the interaction is restricted to two-body terms, interaction matrix elements are “randomized” and therefore the corresponding interaction operator does not commute with the local density. Unlike conventional density–density-type interactions, the SYK-interaction is, in this sense, not integrable. We here investigate a variant of the (complex) SYK model, which restores this integrability. It features a randomized single-body term and a density–density-type interaction. We present numerical investigations suggesting that the model exhibits two integrable phases separated by several intermediate phases including a chaotic one. The chaotic phase carries several characteristic SYK-signatures including in the spectral statistics and the frequency scaling of the Green’s function and therefore should be adiabatically connected to the non-Fermi liquid phase of the original SYK model. Thus, our model Hamiltonian provides a bridge from the SYK-model towards microscopic realism.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Accelerating Multivariate Functional Approximation Computation with Domain Decomposition Techniques⋆

Modeling large datasets through Multivariate Functional Approximations (MFA) provide an elegant way to handle many visualization and scientific analysis workflows. The process necessitates scalable data partitioning methods to compute MFA representations efficiently without compromising the accuracy or continuity of the reconstructed solution. We propose a domain -decomposed method for computing the MFA with B -spline bases, which reduces the total work per task and uses a restricted Additive Schwarz (RAS) method to converge the control point data degrees -of -freedom along subdomain boundaries. We provide an in-depth analysis of the parallel approach with domain decomposition solvers, aiming to minimize local subdomain error residuals and recover high -order continuity at subdomain interfaces with appropriate choices of knot overlaps. The communication cost, determined by the overlap regions in the RAS implementation, is optimized to recover the numerical error profile of the single subdomain case. Our proposed method stands in contrast to previous methods, which typically only recover either C 0 or at best C 1 continuity for arbitrary B -spline degree expansions, or those that require post -processing to blend discontinuities in the reconstructed data. We demonstrate the effectiveness of our approach using analytical and real -world datasets in 1D, 2D, and 3D through both strong and weak scaling studies. The performance results indicate that the overall cost of computing the approximation is directly proportional to the underlying nearest -neighbor communication implementation, and is only weakly dependent on the overlap region size that determines the size of the messages. This finding underscores the efficiency and scalability of our proposed method, making it a promising solution for handling large datasets in scientific workflows.

additive Schwarz solvers↗
DOE OSTI2021

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

A comprehensive ab initio study of periodic actinide–ligand bonding trends for trivalent actinides is performed. Relativistic density functional theory (DFT) and complete active-space (CAS) self-consistent field wavefunction calculations are used to dissect the chemical bonding in the [AnCl 6 ] 3– , [An(CN) 6 ] 3– , [An(NCS) 6 ] 3– , [An(S 2 PMe 2 ) 3 ], [An(DPA) 3 ] 3– , and [An(HOPO)] – series of actinide (An = U–Es) complexes. Except for some differences for the early actinide complexes with DPA, bond orders and excess 5f-shell populations from donation bonding show qualitatively similar trends in 5f n active-space CAS vs DFT calculations. The influence of spin–orbit coupling on donation bonding is small for the tested systems. Along the actinide series, chemically soft vs chemically harder ligands exhibit clear differences in bonding trends. There are pronounced changes in the 5f populations when moving from Pu to Am or Cm, which correlate with previously noted “breaks” in chemical trends. As a result, bonding involving 5f becomes very weak beyond Cm/Bk. We propose that Cm(III) is a borderline case among the trivalent actinides that can be meaningfully considered to be involved in ground-state 5f covalent bonding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗