Search NASA⌕ Search

SEARCH · Search NASA

Results for “complex III”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 955 records · Page 53

A census of gas outflows in type 2 active galactic nuclei

We perform a census of ionized gas outflows using a sample of ∼23,000 type 2 active galactic nuclei (AGNs) out to z ∼ 0.1. By measuring the velocity offset of narrow emission lines, i.e., [O III] λ5007 and Hα, with respect to the systemic velocity measured from the stellar absorption lines, we find that 47% of AGNs display an [O III] line-of-sight velocity offset ≥ 20 km s{sup –1}. The fraction of the [O III] velocity offset in type 2 AGNs is comparable to that in type 1 AGNs after considering the projection effect. AGNs with a large [O III] velocity offset preferentially have a high Eddington ratio, implying that the detected velocity offsets are related to black hole activity. The distribution of the host galaxy inclination is clearly different between the AGNs with blueshifted [O III] and the AGNs with redshifted [O III], supporting the combined model of the biconical outflow and dust obscuration. In addition, for ∼3% of AGNs, [O III] and Hα show comparable large velocity offsets, indicating a more complex gas kinematics than decelerating outflows in a stratified narrow-line region.

79 ASTRONOMY AND ASTROPHYSICS↗

Computational Algorithms for Unit Commitment with AC Power Flows (Final Report)

Security-constrained unit commitment (SCUC) is a key component in power system operations. When AC power flow constraints are considered in the SCUC model (AC-SCUC), the problem becomes extremely difficult due to its discrete and non-convex nature, as described in “Grid Optimization Competition Challenge 3 Problem Formulation (GOCC)”. There are four main challenges: (i) Discrete decisions regarding unit online/offline status and start-up/shut-down procedures for every single unit. The number of discrete decision variables increases considerably when a system integrates multiple generators; (ii) Configuration-based combined-cycle formulations, and multi-commodity models that include ramping products, spin/non-spin products, and regulation up/down products. The combined-cycle units introduce additional discrete decision variables and auxiliary service products further complicate the model by connecting multi-commodity products’ continuous and discrete variables; (iii) SCUC models with AC power flow constraints are far more complex due to massive bilinear terms in the large-scale nonlinear power balance equations. The nonlinear power balance equations are further complicated by the discrete step control variables of shunts; (iv) N − 1 contingency analysis. The size of the model increases linearly with the number of contingencies considered, greatly increasing the size of the optimization model. Accordingly, there is an emergent need to develop a robust algorithm capable of deriving a high-quality solution in a short time and passing through contingency tests simultaneously. In this project, we explore innovative techniques to address this challenging problem by integrating advanced polyhedral theory, approximation methods, relaxation strategies, decomposition techniques, and parallel computing. Each technique approaches the problem from a different perspective, leveraging its specific strengths to tackle distinct challenges. Each individual method has demonstrated its effectiveness in the PI’s previous research. Their integration is expected to significantly reduce the computational time required to solve the proposed complex problem. Successful completion of this project has the potential to transform the industry by enhancing optimization solvers capable of handling large-scale day-ahead energy market clearing models within strict time constraints, while incorporating AC power flow constraints. This advancement will lead to reduced overall generation costs and, consequently, increased social welfare.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Using Statistical Multivariable Models to Understand the Relationship Between Interplanetary Coronal Mass Ejecta and Magnetic Flux Ropes

In-situ measurements of interplanetary coronal mass ejections (ICMEs) display a wide range of properties. A distinct subset, "magnetic clouds" (MCs), are readily identifiable by a smooth rotation in an enhanced magnetic field, together with an unusually low solar wind proton temperature. In this study, we analyze Ulysses spacecraft measurements to systematically investigate five possible explanations for why some ICMEs are observed to be MCs and others are not: i) An observational selection effect; that is, all ICMEs do in fact contain MCs, but the trajectory of the spacecraft through the ICME determines whether the MC is actually encountered; ii) interactions of an erupting flux rope (PR) with itself or between neighboring FRs, which produce complex structures in which the coherent magnetic structure has been destroyed; iii) an evolutionary process, such as relaxation to a low plasma-beta state that leads to the formation of an MC; iv) the existence of two (or more) intrinsic initiation mechanisms, some of which produce MCs and some that do not; or v) MCs are just an easily identifiable limit in an otherwise corntinuous spectrum of structures. We apply quantitative statistical models to assess these ideas. In particular, we use the Akaike information criterion (AIC) to rank the candidate models and a Gaussian mixture model (GMM) to uncover any intrinsic clustering of the data. Using a logistic regression, we find that plasma-beta, CME width, and the ratio O(sup 7) / O(sup 6) are the most significant predictor variables for the presence of an MC. Moreover, the propensity for an event to be identified as an MC decreases with heliocentric distance. These results tend to refute ideas ii) and iii). GMM clustering analysis further identifies three distinct groups of ICMEs; two of which match (at the 86% level) with events independently identified as MCs, and a third that matches with non-MCs (68 % overlap), Thus, idea v) is not supported. Choosing between ideas i) and iv) is more challenging, since they may effectively be indistinguishable from one another by a single in-situ spacecraft. We offer some suggestions on how future studies may address this.

Riley, P.↗

BASTet (Berkeley Analysis and Storage Toolkit)

BASTet is an advanced software library written in Python. BASTet serves as the analysis and storage library for the OpenMSI project. BASTet is an integrate framework for: i) storage of spectral imaging data, ii) storage of derived analysis data, iii) provenance of analyses, iv) integration and execution of analyses via complex workflows. BASTet implements the API for the HDF5 storage format used by OpenMSI. Analyses that are developed using BASTet benefit from direct integration with storage format, automatic tracking of provenance, and direct integration with command-line and workflow execution tools. BASTet also defines interfaces to enable developers to directly integrate their analysis with OpenMSI's web-based viewing infrastruture without having to know OpenMSI. BASTet also provides numerous helper classes and tools to assist with the conversion of data files, ease parallel implementation of analysis algorithms, ease interaction with web-based functions, description methods for data reduction. BASTet also includes detailed developer documentation, user tutorials, iPython notebooks, and other supporting documents.

Bowen, Benjamin↗

Influence of americium complexation on the radiation-induced chemical reactivity of sulfophenyl bistriazinyl pyridine (SO 3 -Ph-BTP) towards the nitrate radical

Sulfophenyl bistriazinyl pyridine (SO 3 -Ph-BTP) is a hydrophilic organic ligand used to separate actinides and lanthanides. Dose accumulation and time-resolved studies have previously provided insight into the radiolytic stability and degradation pathways of SO 3 -Ph-BTP in reprocessing environments, but no study has yet addressed the impact of minor actinide complexation on the radiation chemistry of this ligand. To begin to fill this knowledge gap, a systematic, time-resolved study exploring the reactivity of the nitrate radical (NO 3 • ) with SO 3 -Ph-BTP in the presence of trivalent americium, Am(III), has been conducted, which demonstrates enhanced reactivity (an order of magnitude faster) upon metal complexation.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

Mechanism of Ni-Catalyzed Photochemical Halogen Atom-Mediated C(sp 3 )–H Arylation

Within the context of Ni photoredox catalysis, halogen atom photoelimination from Ni has emerged as a fruitful strategy for enabling hydrogen atom transfer (HAT)-mediated C(sp 3 )–H functionalization. Despite the numerous synthetic transformations invoking this paradigm, a unified mechanistic hypothesis that is consistent with experimental findings on the catalytic systems and accounts for halogen radical formation and facile C(sp 2 )–C(sp 3 ) bond formation remains elusive. We employ kinetic analysis, organometallic synthesis, and computational investigations to decipher the mechanism of a prototypical Ni-catalyzed photochemical C(sp 3 )–H arylation reaction. Our findings revise the previous mechanistic proposals, first by examining the relevance of SET and EnT processes from Ni intermediates relevant to the HAT-based arylation reaction. Our investigation highlights the ability for blue light to promote efficient Ni–C(sp 2 ) bond homolysis from cationic Ni III and C(sp 2 )–C(sp 3 ) reductive elimination from bipyridine Ni II complexes. However interesting, the rates and selectivities of these processes do not account for the productive catalytic pathway. Instead, our studies support a mechanism that involves halogen atom evolution from in situ generated Ni II dihalide intermediates, radical capture by a Ni II (aryl)(halide) resting state, and key C–C bond formation from Ni III . Oxidative addition to Ni I , as opposed to Ni 0 , and rapid Ni III /Ni I comproportionation play key roles in this process. Furthermore, the findings presented herein offer fundamental insight into the reactivity of Ni in the broader context of catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monitoring the Intrinsic Absorption Complex Toward RXJ123.8+0115

The main focus of this study was changed after it became clear that the object to be observed by the Far Ultraviolet Spectroscopic Explorer (FUSE) could not be observed because of spacecraft attitude control system limitations. Therefore, we replaced the prime object for the program (RXJ1230.8+0115) with a secondary object (H1821+643) and began an analysis of a similar quasar spectrum for comparison with the extant RXJ1230.8+0115 spectrum obtained previously by FUSE. Using high-resolution spectra of the radio-quiet, X-ray bright quasar HE0226-4110 obtained with the Hubble Space Telescope (HST) and FUSE, we have examined the remarkable associated absorption line system. The redshift of the quasar is roughly 0.5 so the FUSE+HST spectra cover the rest-frame wavelength in the extreme ultraviolet range 610-1 160A. In this range, we detect transitions from a wide range of ionization species, including the H I Lyman series, Ne VIII, and, for the first time at this resolution, four adjacent stages of oxygen O III-VI. The high quality of these spectra allow us to disentangle the structure of the gas using the complex kinematics to guide the assessments of the multi-component and multi-phase nature of the system. The kinematics of the absorber indicate that all the H I, C 111, and 0 III reside in a single component, while higher ionization species largely arise in a separate, more kinematically complex structure. An analysis of a ground-based spectrum of the quasar covering the H-beta and [0 III] 5007 emission lines reveal excellent agreement in redshift between the 0 III absorption and emission. Thus, for the first time, we are able to use absorption line diagnostics to place interesting constraints on the location and structure of the narrow emission line region around a quasar. In addition, we detect a narrow absorption line that is only seen O VI and lies roughly 50 km/s redward of the narrow emission line component. Absorption from 0 V, and Ne VIII is also detected at this velocity, but as part of broader, more redshifted, component. The line width of this narrow component imply a maximum temperature that is too small to produce O VI through collisional process, suggesting instead that photoionization from the quasar is the dominant ionization mechanism. The photoionization constraints imply that O VII should be the dominant ionization stage in the component.

Sembach, Kenneth↗

Solvothermal synthesis and solid-state characterization of metal-metal bonded tetracarboxylatoditechnetium(II,III) polymers

Investigations of solvothermal reactions with pertechnetate, [TcO 4 ] - , have produced four new low-valent Tc extended metal atom chain (EMAC) complexes with multiple metal-metal bonds. The thermal reaction of potassium pertechnetate with glacial acetic acid, under in-situ hydrogen production from the decomposition of sodium borohydride, yields purple elongated crystals determined to be tetraacetato ditechnetium (II,III) acetate (1), [Tc 2 (O 2 CCH 3 ) 4 (μ-O 2 CCH 3 ] n . Compound 1 was characterized by single crystal X-ray diffraction and its magnetic properties recorded between 10 and 300 K. Single crystal X-ray diffraction analysis of 1 indicates the Tc 2 +5 tetraacetato unit is linked by the carboxylate oxygens of the bridging acetate, similar to known chloride and bromide linkage polymers of composition [Tc 2 (μ-O 2 CCH 3 ) 4 Cl] n , and [Tc 2 (μ-O 2 CCH 3 ) 4 Br] n . Here, using the same synthetic method three similar compounds have been synthesized from propionic, benzoic and pivalic acid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiscale Mathematics for Biomass Conversion to Renewable Hydrogen

The overall objective of this project is to develop multiscale models for understanding and eventually designing complex processes for renewables. To the best of our knowledge, our work is the first attempt at modeling complex reacting systems, whose performance relies on underlying multiscale mathematics. Our specific application lies at the heart of biofuels initiatives of DOE and entails modeling of catalytic systems, to enable economic, environmentally benign, and efficient conversion of biomass into either hydrogen or valuable chemicals. Specific goals include: (i) Development of rigorous spatio-temporal coarse-grained kinetic Monte Carlo (KMC) mathematics and simulation for microscopic processes encountered in biomass transformation. (ii) Development of hybrid multiscale simulation that links stochastic simulation to a deterministic partial differential equation (PDE) model for an entire reactor. (iii) Development of hybrid multiscale simulation that links KMC simulation with quantum density functional theory (DFT) calculations. (iv) Development of parallelization of models of (i)-(iii) to take advantage of Petaflop computing and enable real world applications of complex, multiscale models. In this NCE period, we continued addressing these objectives and completed the proposed work. Main initiatives, key results, and activities are outlined.

08 HYDROGEN↗

A program-level management system for the life cycle environmental and economic assessment of complex building projects

Climate change has become one of the most significant environmental issues, of which about 40% come from the building sector. In particular, complex building projects with various functions have increased, which should be managed from a program-level perspective. Therefore, this study aimed to develop a program-level management system for the life-cycle environmental and economic assessment of complex building projects. The developed system consists of three parts: (i) input part: database server and input data; (ii) analysis part: life cycle assessment and life cycle cost; and (iii) result part: microscopic analysis and macroscopic analysis. To analyze the applicability of the developed system, this study selected ‘U’ University, a complex building project consisting of research facility and residential facility. Through value engineering with experts, a total of 137 design alternatives were established. Based on these alternatives, the macroscopic analysis results were as follows: (i) at the program-level, the life-cycle environmental and economic cost in ‘U’ University were reduced by 6.22% and 2.11%, respectively; (ii) at the project-level, the life-cycle environmental and economic cost in research facility were reduced 6.01% and 1.87%, respectively; and those in residential facility, 12.01% and 3.83%, respective; and (iii) for the mechanical work at the work-type-level, the initial cost was increased 2.9%; but the operation and maintenance phase was reduced by 20.0%. As a result, the developed system can allow the facility managers to establish the operation and maintenance strategies for the environmental and economic aspects from a program-level perspective. - Highlights: • A program-level management system for complex building projects was developed. • Life-cycle environmental and economic assessment can be conducted using the system. • The design alternatives can be analyzed from the microscopic perspective. • The system can be used to establish the optimal O&M strategy at the program-level. • It can be applied to any other country or sector in the global environment.

54 ENVIRONMENTAL SCIENCES↗

CoolPINNs: A physics-informed neural network modeling of active cooling in vascular systems

Emerging technologies like hypersonic aircraft, space exploration vehicles, and batteries avail fluid circulation in embedded microvasculatures for efficient thermal regulation. Modeling is vital during the design and operational phases of these engineered systems. However, many challenges exist in developing a modeling framework. What is lacking is an accurate framework that (i) captures sharp jumps in the thermal flux across complex vasculature layouts, (ii) deals with oblique derivatives (involving tangential and normal components), (iii) handles nonlinearity because of radiative heat transfer, (iv) provides a high-speed forecast for real-time monitoring, and (v) facilitates robust inverse modeling. Here, this paper addresses these challenges by availing the power of physics-informed neural networks (PINNs). We develop a fast, reliable, and accurate Scientific Machine Learning (SciML) framework for vascular-based thermal regulation—called CoolPINNs: a PINNs-based modeling framework for active cooling. The proposed mesh-less framework elegantly overcomes all the mentioned challenges. The significance of the reported research is multi-fold. First, the framework is valuable for real-time monitoring of thermal regulatory systems because of rapid forecasting. Second, researchers can address complex thermoregulation designs since the approach is meshless. Finally, the framework facilitates systematic parameter identification and inverse modeling studies, perhaps the most significant utility of the current framework.

97 MATHEMATICS AND COMPUTING↗

Elusive Intermediates in the Breakdown Reactivity Patterns of Prodrug Platinum(IV) Complexes

Kinetically inert platinum(IV) complexes are receiving growing attention as promising candidates in the effort to develop safe and valid alternatives to classical square-planar Pt(II) complexes currently used in antineoplastic therapy. Their antiproliferative activity requires intracellular Pt(IV)–Pt(II) reduction (activation by reduction). In the present work, a set of five Pt(IV) complexes has been assayed using mass spectrometry–based techniques, i.e., collision-induced dissociation (CID), and IR multiple photon dissociation (IRMPD) spectroscopy, together with ab initio theoretical investigations. Breakdown and reduction mechanisms are observed that lead to Pt(II) species. Evidence is found for typically transient Pt(III) intermediates along the dissociation paths of isolated, negatively charged (electron-rich) Pt(IV) prodrug complexes. .

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Water-soluble Schiff base-actinyl complexes and their effect on the solvent extraction of f-elements

Conventional solvent extraction of selected f-element cations by bis(2-ethylhexyl)phosphoric acid (HDEHP) yields increased extraction from aqueous to organic solution along the series Np(V) < Cm(III) < Eu(III) < U(VI), with distribution ratios all within two orders of magnitude. However, in the presence of the water-soluble tetradentate Schiff base (N,N'-bis(5-sulfonatosalicylidene)-ethylenediamine or H 2 salenSO 3 ), selective complexation of the two actinyl cations (Np(V) and U(VI)) resulted in an extraction order of Np(V) < U(VI) << Eu(III) < Cm(III). The extraction of neither Cm(III) or Eu(III) by HDEHP are significantly impacted by the presence of the aqueous phase Schiff base. Despite observed hydrolytic decomposition of H 2 salenSO 3 in aqueous solutions, the calculated high conditional stability constant (β 11 = 26) for the complex [UO 2 (salenSO 3 )] 2- demonstrates its capacity for aqueous hold-back of U(VI). UV-visible-NIR spectroscopy of solutions prepared with a Np(VI) stock and H 2 salenSO 3 suggest that reduction of Np(VI) to Np(V) by the ligand was rapid, resulting in a pentavalent Np complex that was substantially retained in the aqueous phase. Lastly, results from 1 H NMR of aqueous solutions of H 2 salenSO 3 with U(VI) and La(III), Eu(III), and Lu(III) provides additional evidence that the ligand readily chelates U(VI), but has only weak interactions with trivalent lanthanide ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of Disproportionation in the Dissolution of Mn from Lithium Manganate Spinel

Dissolution of Mn from lithium-manganese spinel has hindered its commercialization as a cathode material in Li-ion batteries. Disproportionation of near-surface Mn(III), in the presence of acid, has been widely thought to result in dissolved divalent Mn. To what extent stray acidic water in the cell (as opposed to the organic electrolyte) acts as the solvent for Mn ions has not been established. Simulations by Leung show that a small displacement of trivalent Mn from its equilibrium site at an LiMn 2 O 4 (001)/ ethylene carbonate interface leads to its reduction to Mn(II). In the present work, Thermodynamic Integration is performed, based on first-principles molecular dynamics simulations within the Blue-Moon ensemble, for the detachment of Mn(III) ions at the LiMn 2 O 4 (001)/water interface. The results show that reduction of Mn(III) to Mn(II) occurs also in the case of an aqueous interface. The simulations were performed for both neutral and acidic water (in the presence of HF), with the coordination number of the dissolving Mn ion with substrate oxygen ions taken as the reaction coordinate. The simulations indicate that an F - ion strongly binds to a surface Mn(III) ion, and weakens its adhesion to the substrate. Owing to this weakening, a surface Mn-F complex traverses regions of phase space at room temperature where disproportionation becomes energetically favorable. Although this disproportionation occurs close to the substrate, where the Mn coordination number is only slightly lowered from its equilibrium value, we argue that the likelihood of reattachment after disproportionation is small (Leung arrived at a similar interpretation in the case of the LiMn 2 O 4 (001)/ EC interface). We suggest that the critical role of F - in promoting dissolution is to weaken the Mn binding to the substrate so as to enable disproportionation. The partially detached MnF complex may then undergo additional interaction with the solvent to form, e.g., MnF 2 , which would enable transport away from the substrate. In conclusion, the EPR measurements by Shilina et al. which appear to show Mn(III) as the predominant solvated species are discussed.

25 ENERGY STORAGE↗

Spontaneous electromagnetic fluctuations in unmagnetized plasmas. II. Relativistic form factors of aperiodic thermal modes

General expressions for the electromagnetic fluctuation spectra in unmagnetized plasmas are derived using fully relativistic dispersion functions and form factors for the important class of isotropic plasma particle distribution functions including in particular relativistic Maxwellian distributions. In order to obtain fluctuation spectra valid in the entire complex frequency plane, the proper analytical continuations of the unmagnetized form factors and dispersion functions are presented. The results are illustrated for the important special case of isotropic Maxwellian particle distribution functions providing in particular the thermal fluctuations of aperiodic modes. No restriction to the plasma temperature value is made, and the electromagnetic fluctuation spectra of ultrarelativistic thermal plasmas are calculated. The fully relativistic calculations also provide more general results in the limit of nonrelativistic plasma temperatures being valid in the entire complex frequency plane. They complement our earlier results in paper I and III of this series for negative values of the imaginary part of the frequency. A new collective, transverse, damped aperiodic mode with the damping rate γ∝−k{sup −5/3} is discovered in an isotropic thermal electron-proton plasma with nonrelativistic temperatures.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys

A simple analytical procedure is described for accurately and precisely determining the zirconium or hafnium content of molybdenum-base alloys. The procedure is based on the reaction of the reagent Arsenazo III with zirconium or hafnium in strong hydrochloric acid solution. The colored complexes of zirconium or hafnium are formed in the presence of molybdenum. Titanium or rhenium in the alloy have no adverse effect on the zirconium or hafnium complex at the following levels in the selected aliquot: Mo, 10 mg; Re, 10 mg; Ti, 1 mg. The spectrophotometric measurement of the zirconium or hafnium complex is accomplished without prior separation with a relative standard deviation of 1.3 to 2.7 percent.

Dupraw, W. A.↗

A High Signal-To-Noise Ultraviolet Spectrum of NGC 7469: New Support for Reprocessing of Continuum Radiation

From 1996 June 10 to 1996 July 29, the International AGN Watch monitored the Seyfert 1 galaxy NGC 7469 using the International Ultraviolet Explorer, the Rossi X-Ray Timing Explorer, and a network of ground-based observatories. On 1996 June 18, in the midst of this intensive monitoring period, we obtained a high signal-to-noise snapshot of the UV spectrum from 1150 to 3300 A, using the Faint Object Spectrograph (FOS) on the Hubble Space Telescope. This spectrum allows us to disentangle the UV continuum more accurately from the broad wings of the emission lines, to identify clean continuum windows free of contaminating emission and absorption, and to deblend line complexes such as Ly(alpha) + N V, C IV + He II + O III], Si III] + C III], and Mg II + Fe II. Using the FOS spectrum as a template, we have fitted and extracted line and continuum fluxes from the IUE monitoring data. The cleaner continuum extractions c o n h the discovery of time delays between the different UV continuum bands by Wanders et al. Our new measurements show delays increasing with wavelength for continuum bands centered at 1485, 1740, and 1825 A, relative to 1315 A with delays of 0.09, 0.28, and 0.36 days, respectively. Like many other Seyfert I galaxies, the UV spectrum of NGC 7469 shows intrinsic, blue-shifted absorption in Ly(alpha), N V, and C IV. Soft X-ray absorption is also visible in archival ASCA X-ray spectra. The strength of the UV absorption, however, is not compatible with a single-zone model in which the same material absorbs both the UV and X-ray light. Similar to other Seyfert galaxies, such as NGC 3516, the UV-absorbing gas in NGC 7469 has a lower ionization parameter and column density than the X-ray-absorbing material. While the UV and X-ray absorption does not arise in the same material, the frequent occurrence of both associated UV absorption and X-ray warm absorbers in the same galaxies suggests that the gas supply for each has a common origin.

Kriss, Gerard A.↗