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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

A comprehensive approach for elucidating the interplay between 4f n +1 and 4f n 5d 1 configurations in Ln 2+ complexes

Lanthanides (Ln) are typically found in the +3 oxidation state. However, in recent decades, their chemistry has been expanded to include the less stable +2 oxidation state across the entire series except promethium (Pm), facilitated by the coordination of ligands such as trimethylsilylcyclopentadienyl, C 5 H 4 SiMe 3 (Cp'). The [LnCp' 3 ] complexes have been the workhorse for the synthesis and theoretical study of the fundamental aspects of divalent lanthanide chemistry, where experimental and computational evidence have suggested the existence of different ground state (GS) configurations, 4f n+1 or 4f n 5d 1 , depending on the specific metal. Standard reduction potentials and 4f n+1 to 4f n 5d 1 promotion energies have been two factors usually considered to rationalize the occurrence of these variable GS configurations, however the driving force behind this phenomenon is still not clear. In this work we present a comprehensive theoretical approach to shed light on this matter using the [LnCp 3 ] - model systems. We begin by calculating 4f n+1 to 4f n 5d 1 promotion energies and successfully correlate them with existing experimental data. Furthermore, we analyze how changes in the GS charge distribution between the Ln ions, LnCp 3 and the reduced [LnCp 3 ] - complexes (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) correlate with experimental trends in redox potentials and the calculated promotion energies. For this purpose, a comprehensive theoretical work that includes relativistic ligand field density functional theory (LFDFT) and relativistic ab initio wavefunction methods was performed. This study will help the rational design of suitable environments to tune the different GS configurations as well as modulating the spectroscopic properties of new Ln 2+ complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Nonlinear zero-sum differential game analysis by singular perturbation methods

A class of nonlinear, zero-sum differential games, exhibiting time-scale separation properties, can be analyzed by singular-perturbation techniques. The merits of such an analysis, leading to an approximate game solution, as well as the 'well-posedness' of the formulation, are discussed. This approach is shown to be attractive for investigating pursuit-evasion problems; the original multidimensional differential game is decomposed to a 'simple pursuit' (free-stream) game and two independent (boundary-layer) optimal-control problems. Using multiple time-scale boundary-layer models results in a pair of uniformly valid zero-order composite feedback strategies. The dependence of suboptimal strategies on relative geometry and own-state measurements is demonstrated by a three dimensional, constant-speed example. For game analysis with realistic vehicle dynamics, the technique of forced singular perturbations and a variable modeling approach is proposed. Accuracy of the analysis is evaluated by comparison with the numerical solution of a time-optimal, variable-speed 'game of two cars' in the horizontal plane.

Sinar, J.↗
NASA NTRS2006

The Potential of Water Vapor & Precipitation Estimation with a Differential-frequency Radar

In the presence of rain, the radar return powers from a three-frequency radar, with center frequency at 22.235 GHz and upper and lower frequencies chosen with equal water vapor absorption coefficients, can be used to estimate water vapor density and parameters of the precipitation. A linear combination of differential measurements between the center and lower frequencies on one hand and the upper and lower frequencies on the other provide an estimate of differential water vapor absorption. Conversely, the difference in radar reflectivity factors (in dB) between the upper and lower frequencies is independent of water vapor absorption and can be used to estimate the median mass diameter of the hydrometeors. For a down-looking radar, path-integrated estimates of water vapor absorption may be possible under rain-free as well as raining conditions by using the surface returns at the three frequencies. Cross-talk or interference between the precipitation and water vapor estimates depends on the frequency separation of the channels as well as on the phase state and the median mass diameter of the hydrometeors. Simulations of the retrieval of water vapor absorption show that the largest source of variability arises from the variance in the measured radar return powers while the largest biases occur in the mixed-phase region. Use of high pulse repetition frequencies and signal whitening methods may be needed to obtain the large number of independent samples required. Measurements over a fractional bandwidth, defined as the ratio of the difference between the upper and lower frequencies to the center frequency, up to about 0.2 should be passible in a differential frequency mode, where a single transceiver and antenna are used. Difficulties in frequency allocation may require alternative choices of frequency where the water vapor absorptions at the low and high frequencies are unequal. We consider the degradation in the retrieval accuracy when the frequencies are not optimum.

Meneghini, Robert↗
NASA NTRS1994

Vector quantization for efficient coding of upper subbands

This paper examines the application of vector quantization (VQ) to exploit both intra-band and inter-band redundancy in subband coding. The focus here is on the exploitation of inter-band dependency. It is shown that VQ is particularly suitable and effective for coding the upper subbands. Three subband decomposition-based VQ coding schemes are proposed here to exploit the inter-band dependency by making full use of the extra flexibility of VQ approach over scalar quantization. A quadtree-based variable rate VQ (VRVQ) scheme which takes full advantage of the intra-band and inter-band redundancy is first proposed. Then, a more easily implementable alternative based on an efficient block-based edge estimation technique is employed to overcome the implementational barriers of the first scheme. Finally, a predictive VQ scheme formulated in the context of finite state VQ is proposed to further exploit the dependency among different subbands. A VRVQ scheme proposed elsewhere is extended to provide an efficient bit allocation procedure. Simulation results show that these three hybrid techniques have advantages, in terms of peak signal-to-noise ratio (PSNR) and complexity, over other existing subband-VQ approaches.

Zeng, W. J.↗
NASA NTRS2026

Development, Characterization, and Validation of Elevated-Temperature Constitutive Models: Deformation and Damage

This report provides a brief review of experimentally observed hereditary and nonhereditary material behavior along with background information on standard as well as advanced internal state variable constitutive modeling at elevated temperature. A description of exploratory, characterization, and validation testing is presented along with a detailed outline of what constitutes “sufficient” data content (i.e., quality and quantity) for developing or enhancing, characterizing, and validating a particular sophisticated nonlinear time- and history-dependent (hereditary) class of constitutive models known as GVIPS (generalized viscoplasticity with potential structure). The tests described are necessary to reveal a material’s behavior in the reversible (or viscoelastic) and irreversible (or viscoplastic) regimes, for the identification of both deformation and damage model parameters. Results presented are primarily for metallic materials. In all cases, both uniaxial and multiaxial tests are described, and the linkage between the specific tests and the parameters within the model that can be characterized from the results of these tests are also discussed. Discussion is also provided relative to the role information management must play relative to material data collection, analysis, maintenance, and dissemination. The need for such an information system is particularly important as both analyst and designer move toward utilizations of sophisticated, nonlinear time- and history dependent (hereditary) constitutive models. Lastly, the concept of state space and its utility in understanding and establishing constitutive models is addressed throughout. The intent behind this document is to help both the modeler and experimentalist understand each other’s specific points of view and provide guidance for both model development and characterization. Emphasis has been placed on providing the mechanician with information regarding how tests are performed and what issues to be aware of when interpreting results. It is hoped that experimentalists will take away a new perspective on the types of information that modelers and analysts are looking for from them.

Constitutive Modeling↗
DOE OSTI2024

Constraining Present‐Day Anthropogenic Total Iron Emissions Using Model and Observations

Abstract Iron emissions from human activities, such as oil combustion and smelting, affect the Earth's climate and marine ecosystems. These emissions are difficult to quantify accurately due to a lack of observations, particularly in remote ocean regions. In this study, we used long‐term, near‐source observations in areas with a dominance of anthropogenic iron emissions in various parts of the world to better estimate the total amount of anthropogenic iron emissions. We also used a statistical source apportionment method to identify the anthropogenic components and their sub‐sources from bulk aerosol observations in the United States. We find that the estimates of anthropogenic iron emissions are within a factor of 3 in most regions compared to previous inventory estimates. Under‐ or overestimation varied by region and depended on the number of sites, interannual variability, and the statistical filter choice. Smelting‐related iron emissions are overestimated by a factor of 1.5 in East Asia compared to previous estimates. More long‐term iron observations and the consideration of the influence of dust and wildfires could help reduce the uncertainty in anthropogenic iron emissions estimates.

Meteorology & Atmospheric Sciences↗
NASA NTRS1991

One shot methods for optimal control of distributed parameter systems 1: Finite dimensional control

The efficient numerical treatment of optimal control problems governed by elliptic partial differential equations (PDEs) and systems of elliptic PDEs, where the control is finite dimensional is discussed. Distributed control as well as boundary control cases are discussed. The main characteristic of the new methods is that they are designed to solve the full optimization problem directly, rather than accelerating a descent method by an efficient multigrid solver for the equations involved. The methods use the adjoint state in order to achieve efficient smoother and a robust coarsening strategy. The main idea is the treatment of the control variables on appropriate scales, i.e., control variables that correspond to smooth functions are solved for on coarse grids depending on the smoothness of these functions. Solution of the control problems is achieved with the cost of solving the constraint equations about two to three times (by a multigrid solver). Numerical examples demonstrate the effectiveness of the method proposed in distributed control case, pointwise control and boundary control problems.

Taasan, Shlomo↗
DOE OSTI2026

Software Control Program For Transportable Microgrid State-of-charge Balancing And Frequency Stability Controls

A deterministic state-of-charge (SOC) balancing approach software control code is introduced as an integral secondary management to primary control layer of an islanded small microgrid or nanogrid system made up of multiple grid-forming inverter/battery/solar combination systems, where each set of batteries with each inverter are on independent DC buses (i.e. non-paralleled on the DC sides). A DERMS-level control approach, algorithm and automation controller program was developed to improve coordination and enable microgrid asset compliance and SOC balancing, enabling provision of a system-level power stability support architecture, load support, and asset scalability. The architecture is configured to treat each unit or micro/nano-grid as a node in a microgrid network, allowing for autonomous DERMS control regarding load and SOC balancing and power stability. As the network grows with the addition of units, greater coordination efforts may be required. The ideal small network microgrid ranges from 2-10 inverter/battery units before additional control parameters must be considered in the existing architecture. The control approach focuses on a deterministic state-of-charge analysis as the primary level control process followed by a secondary control loop using a forced frequency-watt droop strategy to conform off-the-shelf components into behaving under a leader-follower configuration. Adopting this control scheme has been shown to allow for a balanced, unit-coordinated microgrid network, enabling stable power flow. The deterministic state-of-charge approach is introduced as an integral primary control layer of an islanded small network microgrid. A standard strategy for SOC balancing is implementing a battery management system (BMS) to control SOC on the DC side. An alternative approach is to determine how to coordinate sending and receiving power on the AC side with multiple units. The latter approach assesses all the integrated units in the microgrid network. Once the individual units are identified, further system data is required to calculate each unit's total kWh, provided information about its capability to supply or consume kWh and availability. The secondary control layer in the multi-layered small network microgrid methodology uses the primary layer’s decision to initiate frequency setpoint changes, initializing the SOC balancing. The secondary control layer considers numerous system-dependent variables to enable a charging and discharging profile based on adjustable frequency setpoints. The combined architecture will result in stable, coordinated power flow enhancing an AC microgrid's functionalities.

Myers, KurtS [Idaho National Laboratory (INL), Ida↗
DOE OSTI2026

Interfacial Charge Transfer Pathways in Photoelectrochemical H 2 Evolution by a Single-Component Molecular Catalyst on a Conductive Metal Oxide

Dye-sensitized photoelectrosynthesis cells traditionally combine a photosensitizing dye to harvest light and a catalyst to generate chemical fuels on a semiconductor. Here, in this work, a photoactive catalyst capable of both light absorption and fuel formation, [Cp*Ir(4,4′-Y 2 -bpy)Cl][Cl] (Cp* = pentamethylcyclopentadienyl, bpy = 2,2′-bipyridine, Y = CH 2 PO 3 H 2 ), is anchored to a mesoporous tin-doped indium oxide (ITO) electrode and facilitates photoelectrochemical H 2 evolution in water without the need for additional photosensitizers or sacrificial reductants. Spectroelectrochemistry indicates a single-site H 2 evolution mechanism involving charge injection to ITO, in contrast to the bimetallic mechanism observed in solution. Cyclic voltammetry and variable-potential chronoamperometry under illumination probe competing pathways via interfacial electron transfer between the Ir hydride excited state and the conductive ITO electrode. A Marcus theory framework provides reorganization energies for competing interfacial electron transfer pathways from potential-dependent quantum yield measurements. The light-driven H 2 evolution catalysis on conducting oxide proceeds with high Faradaic efficiency and current densities comparable to photoelectrodes utilizing p-type semiconductors. By uncovering the principal electron transfer pathways that govern photocatalytic efficiency, this study establishes design principles for hybrid molecular photoelectrocatalysts.

catalysts↗
DOE OSTI2024

East Pacific ENSO Offers Early Predictive Signals for Harvest Yields

Abstract Annual wheat yields have steadily risen over the past century, but harvests remain highly variable and dependent on myriad weather conditions during a long growing season. In Kansas, for example, the 2014 crop year brought the lowest average yield in decades at 28 bushels per acre, while in 2016 farmers in the Wheat State, as Kansas is often called, enjoyed a historic high of 57 bushels per acre. It is broadly known that remote forces like El Niño–Southern Oscillation contribute to meteorological outcomes across North America, including in the wheat-growing regions of the U.S. Midwest, but the differential imprints of ENSO phases and flavors have not been well explored as leading indicators for harvest outcomes in highly specific agricultural regions, such as the more than 7 million acres upon which wheat is grown in Kansas. Here, we demonstrate a strong, steady, and long-term association between a simple “wheat yield index” and sea surface temperature anomalies, more than a year earlier, in the East Pacific, potentially offering insights into forthcoming harvest yields several seasons before planting commences.

Meteorology & Atmospheric Sciences↗
NASA NTRS1974

Geodesic synchrotron radiation in the Kerr geometry by the method of asymptotically factorized Green's functions

The scalar, electromagnetic, and gravitational geodesic-synchrotron-radiation (GSR) spectra are determined for the case of a test particle moving on a highly relativistic circular orbit about a rotating (Kerr) black hole. It is found that the spectral shape depends only weakly on the value of the angular-momentum parameter (a/M) of the black hole, but the total radiated power drops unexpectedly for a value of at least 0.95 and vanishes as the value approaches unity. A spin-dependent factor (involving the inner product of the polarization of a radiated quantum with the source) is isolated to explain the dependence of the spectral shape on the spin of the radiated field. Although the scalar wave equation is solved by separation of variables, this procedure is avoided for the vector and tensor cases by postulating a sum-over-states expansion for the Green's function similar to that found to hold in the scalar case. The terms in this sum, significant for GSR, can then be evaluated in the geometric-optics approximation without requiring the use of vector or tensor spherical harmonics.

Chrzanowski, P. L.↗
NASA NTRS1989

Predictions of Poisson's ratio in cross-ply laminates containing matrix cracks and delaminations

A damage-dependent constitutive model for laminated composites has been developed for the combined damage modes of matrix cracks and delaminations. The model is based on the concept of continuum damage mechanics and uses second-order tensor valued internal state variables to represent each mode of damage. The internal state variables are defined as the local volume average of the relative crack face displacements. Since the local volume for delaminations is specified at the laminate level, the constitutive model takes the form of laminate analysis equations modified by the internal state variables. Model implementation is demonstrated for the laminate engineering modulus E(x) and Poisson's ratio nu(xy) of quasi-isotropic and cross-ply laminates. The model predictions are in close agreement to experimental results obtained for graphite/epoxy laminates.

Harris, Charles E.↗
NASA NTRS2010

Electrically Variable Resistive Memory Devices

Nonvolatile electronic memory devices that store data in the form of electrical- resistance values, and memory circuits based on such devices, have been invented. These devices and circuits exploit an electrically-variable-resistance phenomenon that occurs in thin films of certain oxides that exhibit the colossal magnetoresistive (CMR) effect. It is worth emphasizing that, as stated in the immediately preceding article, these devices function at room temperature and do not depend on externally applied magnetic fields. A device of this type is basically a thin film resistor: it consists of a thin film of a CMR material located between, and in contact with, two electrical conductors. The application of a short-duration, low-voltage current pulse via the terminals changes the electrical resistance of the film. The amount of the change in resistance depends on the size of the pulse. The direction of change (increase or decrease of resistance) depends on the polarity of the pulse. Hence, a datum can be written (or a prior datum overwritten) in the memory device by applying a pulse of size and polarity tailored to set the resistance at a value that represents a specific numerical value. To read the datum, one applies a smaller pulse - one that is large enough to enable accurate measurement of resistance, but small enough so as not to change the resistance. In writing, the resistance can be set to any value within the dynamic range of the CMR film. Typically, the value would be one of several discrete resistance values that represent logic levels or digits. Because the number of levels can exceed 2, a memory device of this type is not limited to binary data. Like other memory devices, devices of this type can be incorporated into a memory integrated circuit by laying them out on a substrate in rows and columns, along with row and column conductors for electrically addressing them individually or collectively.

Liu, Shangqing↗
DOE OSTI2024

Compound Flooding in Halmstad: Common Causes, Interannual Variability and the Effects of Climate Change

Compound flooding was investigated in Halmstad on the Swedish west coast. The highest sea level ever recorded in Sweden was recorded by the Halmstad tide gauge. Moreover, through the city runs Nissan, one of the largest hydropower-producing rivers in southern Sweden. Together these features make the city an interesting location to study compound flooding. Co-variability between different hazards are studied using a unique set of downscaled climate scenario projections produced using state-of-the-art regional atmosphere, ocean and hydrological models. River discharge and sea level annual maxima are found to be correlated with peak strength on interannual time scales. This co-variability is found to derive from a mutual dependence that these hazards have on the North Atlantic Oscillation (NAO). Precipitation also shares this dependence in winter months and acts as a driver, building up the fluvial river hazard, while potentially adding additional pluvial hazard. Trends are also assessed, and it was found that future changes in compound flooding will most likely be driven primarily by mean sea level rise and secondarily by increases in mean river discharge.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1981

Theory of satellite orbit-orbit resonance

On the basis of the strong mathematical and physical parallels between orbit-orbit and spin-orbit resonances, the dynamics of mutual orbit perturbations between two satellites about a massive planet are examined, exploiting an approach previously adopted in the study of spin-orbit coupling. Resonances are found to exist when the mean orbital periods are commensurable with respect to some rotating axis, which condition also involves the apsidal and nodal motions of both satellites. In any resonant state the satellites are effectively trapped in separate potential wells, and a single variable is found to describe the simultaneous librations of both satellites. The librations in longitude are 180 deg out-of-phase, with fixed amplitude ratio that depends only on their relative masses and semimajor axes. The theory is applicable to Saturn's resonant pairs Titan-Hyperion and Mimas-Tethys, and in these cases the calculated libration periods are in reasonably good agreement with the observed periods.

Blitzer, L.↗
NASA NTRS1988

A viscoplastic theory applied to copper

A phenomenologically based viscoplastic model is derived for copper. The model is thermodynamically constrained by the condition of material dissipativity. Two internal state variables are considered. The back stress accounts for strain-induced anisotropy, or kinematic hardening. The drag stress accounts for isotropic hardening. Static and dynamic recovery terms are not coupled in either evolutionary equation. The evolution of drag stress depends on static recovery, while the evolution of back stress depends on dynamic recovery. The material constants are determined from isothermal data. Model predictions are compared with experimental data for thermomechanical test conditions. They are in good agreement at the hot end of the loading cycle, but the model overpredicts the stress response at the cold end of the cycle.

Freed, Alan D.↗
NASA NTRS1997

Visualization of Unsteady Computational Fluid Dynamics

The current compute environment that most researchers are using for the calculation of 3D unsteady Computational Fluid Dynamic (CFD) results is a super-computer class machine. The Massively Parallel Processors (MPP's) such as the 160 node IBM SP2 at NAS and clusters of workstations acting as a single MPP (like NAS's SGI Power-Challenge array and the J90 cluster) provide the required computation bandwidth for CFD calculations of transient problems. If we follow the traditional computational analysis steps for CFD (and we wish to construct an interactive visualizer) we need to be aware of the following: (1) Disk space requirements. A single snap-shot must contain at least the values (primitive variables) stored at the appropriate locations within the mesh. For most simple 3D Euler solvers that means 5 floating point words. Navier-Stokes solutions with turbulence models may contain 7 state-variables. (2) Disk speed vs. Computational speeds. The time required to read the complete solution of a saved time frame from disk is now longer than the compute time for a set number of iterations from an explicit solver. Depending, on the hardware and solver an iteration of an implicit code may also take less time than reading the solution from disk. If one examines the performance improvements in the last decade or two, it is easy to see that depending on disk performance (vs. CPU improvement) may not be the best method for enhancing interactivity. (3) Cluster and Parallel Machine I/O problems. Disk access time is much worse within current parallel machines and cluster of workstations that are acting in concert to solve a single problem. In this case we are not trying to read the volume of data, but are running the solver and the solver outputs the solution. These traditional network interfaces must be used for the file system. (4) Numerics of particle traces. Most visualization tools can work upon a single snap shot of the data but some visualization tools for transient problems require dealing with time.

Haimes, Robert↗