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At least 1,207 records · Page 67
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Cosmic structure formation

This article reviews the prevailing paradigm for how galaxies and larger structures formed in the universe: gravitational instability. Basic observational facts are summarized to motivate the standard cosmological framework underlying most detailed investigations of structure formation. The observed univers approaches spatial uniformity on scales larger than about 10(exp 26) cm. On these scales gravitational dynamics is almost linear and therefore relatively easy to relate to observations of large-scale structure. On smaller scales cosmic structure is complicated not only by nonlinear gravitational clustering but also by nonlinear nongravitational gas dynamical processes. The complexity of these phenomena makes galaxy formation one of the grand challenge problems of the physical sciences. No fully satisfactory theory can presently account in detail for the observed cosmic structure. However, as this article summarizes, significant progress has been made during the last few years.

Bertschinger, Edumund↗
NASA NTRS2009

The Influence of Obliquity on Europan Cycloid Formation

Tectonic patterns on Europa are influenced by tidal stress. An important well-organized component is associated with the orbital eccentricity, which produces a diurnally varying stress as Jupiter's apparent position in Europa's sky oscillates in longitude. Cycloidal lineaments seem to have formed as cracks propagated in this diurnally varying stress field. Maps of theoretical cycloid patterns capture many of the characteristics of the observed distribution on Europa. However, a few details of the observed cycloids distribution have not reproduced by previous models. Recently, it has been shown that Europa has a finite forced obliquity, so Jupiter's apparent positon in Europa's sky will also oscillate in latitude. We explore this new type of diurnal effect on cycloid formation. We find that stress from obliquity may be the key to explaining several characteristics of observed cycloids such as the shape of equator-crossing cycloids and the shift in the crack patterns in the Argadnel Regio region. All of those improvements of the fit between observaiton and theory seem to require Jupiter crossing Europa's equatorial plane 45 deg. to 180 deg after perijove passage. Suggestive of complex orbital dynamics that lock the direction of Europe's pericenter with the direction of the ascending node at the time these cracks were formed.

Hurford, T. a.↗
NASA NTRS2010

Augmented Adaptive Control of a Wind Turbine in the Presence of Structural Modes

Wind turbines operate in highly turbulent environments resulting in aerodynamic loads that can easily excite turbine structural modes, potentially causing component fatigue and failure. Two key technology drivers for turbine manufacturers are increasing turbine up time and reducing maintenance costs. Since the trend in wind turbine design is towards larger, more flexible turbines with lower frequency structural modes, manufacturers will want to develop methods to operate in the presence of these modes. Accurate models of the dynamic characteristics of new wind turbines are often not available due to the complexity and expense of the modeling task, making wind turbines ideally suited to adaptive control. In this paper, we develop theory for adaptive control with rejection of disturbances in the presence of modes that inhibit the controller. We use this method to design an adaptive collective pitch controller for a high-fidelity simulation of a utility-scale, variable-speed wind turbine operating in Region 3. The objective of the adaptive pitch controller is to regulate generator speed, accommodate wind gusts, and reduce the interference of certain structural modes in feedback. The control objective is accomplished by collectively pitching the turbine blades. The adaptive pitch controller for Region 3 is compared in simulations with a baseline classical Proportional Integrator (PI) collective pitch controller.

Frost, Susan A.↗
NASA NTRSDate not supplied

Variational Coupled Loads Analysis using the Hybrid Parametric Variation Method

Time-domain coupled loads analysis (CLA)is used to determine the response of a launch vehicle and payload system to transient forces, such as liftoff, engine ignitions and shutdowns, jettison events, and atmospheric flight loads, such as buffet. CLA, using Hurty/Craig-Bampton (HCB)component models, is the accepted method for the establishment of design-level loads for launch systems. However, uncertainty in the component models flows into uncertainty in predicted system results. Uncertainty in the structural responses during launch is a significant concern because small variations in launch vehicle and payload mode shapes and their interactions can result in significant variations in system loads. Uncertainty quantification (UQ)is used to determine statistical bounds on prediction accuracy based on model uncertainty. In this paper uncertainty is treated at the HCB component-model level. In an effort to account for model uncertainties and statistically bound their effect on CLA predictions, this work combines CLA with UQ in a process termed variational coupled loads analysis (VCLA). The modeling of uncertainty using a parametric approach, in which input parameters are represented by random variables, is common, but its major drawback is the resulting uncertainty is limited to the form of the nominal model. Uncertainty in model form is one of the biggest contributors to uncertainty in complex built-up structures. Model-form uncertainty can be represented using a nonparametric approach based on random matrix theory (RMT). In this work, UQ is performed using the hybrid parametric variation (HPV)method, which combines parametric with nonparametric uncertainty at the HCB component model level. The HPV method requires the selection of dispersion values for the HCB fixed-interface (FI)eigenvalues, and the HCB mass and stiffness matrices. The dispersions are based upon component test-analysis modal correlation results. During VCLA, random component models are assembled into an ensemble of random systems using a Monte Carlo (MC)approach. CLA is applied to each of the ensemble members to produce an ensemble of system-level responses for statistical analysis. The proposed methodology is demonstrated through its application to a buffet loads analysis of NASA’s Space Launch System (SLS)during the transonic regime fifty seconds after liftoff. Core stage (CS)section shears and moments are recovered, and statistics are computed.

Uncertainty Quantification↗
DOE OSTI2020

Theoretical insight into thermodynamics of particle-based crystallization

Crystallization process often does not follow the monomer-by-monomer addition pathway, as described by classical nucleation theory. Instead, initial step may involve the formation of larger building blocks, such as crystalline or amorphous nanoparticles, droplets, clusters, complexes or oligomers, which subsequently undergo assembly into a crystal. These multistep crystallization processes are ubiquitous in mineral formation and biomineralization. In materials synthesis utilizing non-classical crystallization pathways is particularly attractive as the restriction on which crystalline faces can grow is lifted in a multistep crystallization process adding to the versatility of materials architectures that can be obtained. Predicting the outcomes of non-classical crystallization through the understanding of the control parameters influencing crystallization pathways is an important and challenging task essential for utilizing the full potential of non-classical crystallization in the design of functional materials. Here, the current status of the development of a predictive theoretical framework for modeling non-classical crystallization is reviewed.

Sushko, Maria L.↗
DOE OSTI2020

Quantifying Uncertainties of Microscopic Nuclear Theories

The goal of this project was to produce modernized nuclear data libraries of light ion fusion reactions and actinide fission product yields. Such libraries are essential input in both stockpile science but also fundamental science (nucleosynthesis, superheavy nuclei). When such libraries are used to model complex processes involving exotic, very short-lived nuclei that have not been measured experimentally, the underlying nuclear data come from theoretical models, the predictive power of which needs to be quantified, together with its uncertainties. By teaming up nuclear theorists and statisticians, we built comprehensive theoretical frameworks based on the most fundamental theories of fusion and fission that we coupled for the first time with a Bayesian framework with machine learning techniques for uncertainty quantification. Our results include: (1) statistical emulators for neutron-alpha scattering, and the fission product mass yields of neutron-induced fission of 239 Pu, which will enable developers to generate random realizations of the corresponding data for uncertainty quantification (UQ) in applications; (2) the first complete and most accurate ab initio prediction of the S-factor for proton capture on 7 Be, which – combined with UQ – may become the recommended value at solar energies in the next review of solar fusion cross sections; (3) statistical emulators for fission mass yields in the neutron-induced fission of 239 Pu; (4) the first quantification of how uncertainties in nuclear forces impact fission properties that are relevant in nucleosynthesis simulations to explain how heavy elements are formed in the Cosmos.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Ab Initio Study of Vibronic and Magnetic 5f-to-5f and Dipole-Allowed 5f-to-6d and Charge-Transfer Transitions in [UX 6 ] n – (X = Cl, Br; n = 1, 2)

The absorption spectra of the octahedral [UX 6 ] n– (X = Cl, Br; n = 1, 2) complexes in the near-infrared (NIR) and UV–vis spectral regions were studied theoretically, using a relativistic restricted active space second-order perturbation theory (RASPT2) wavefunction framework, with the spin–orbit (SO) coupling treated by state interaction, in conjunction with Kohn–Sham density functional theory calculations for determining the vibrational normal modes. The electric-dipole-allowed ligand-to-metal charge-transfer (LMCT) and 5f-to-6d transitions, and the electric-dipole-forbidden 5f-to-5f ligand field (LF) transitions, are thereby obtained within the same theoretical framework. For the 5f-to-5f LF transitions, the observed absorption intensity is mostly due to vibronic coupling with low-energy electric-dipole-allowed transitions, but in some cases, the magnetic dipole intensity of the purely electronic transition has comparable intensity to the vibronic transitions. Here, experimental LF spectra of 5f 2 open-shell systems have been reported decades back, but ab initio calculations of their vibronic intensity have not yet been reported in the literature. Although the LF spectra for the 5f 2 systems can be assigned in detail, based on the calculations, the spectra are very complex and the underlying electronic states are strongly multiconfigurational. Therefore, the usefulness of the LF spectra beyond serving as a “fingerprint” of the LF and the metal oxidation state appears to be limited.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Modeling of Wall-Bounded Complex Flows and Free Shear Flows

Various wall-bounded flows with complex geometries and free shear flows have been studied with a newly developed realizable Reynolds stress algebraic equation model. The model development is based on the invariant theory in continuum mechanics. This theory enables us to formulate a general constitutive relation for the Reynolds stresses. Pope was the first to introduce this kind of constitutive relation to turbulence modeling. In our study, realizability is imposed on the truncated constitutive relation to determine the coefficients so that, unlike the standard k-E eddy viscosity model, the present model will not produce negative normal stresses in any situations of rapid distortion. The calculations based on the present model have shown an encouraging success in modeling complex turbulent flows.

Shih, Tsan-Hsing↗
DOE OSTI2020

CO 2 Hydrogenation and Formic Acid Dehydrogenation Using Ir Catalysts with Amide-Based Ligands

In this work, a series of Ir catalysts bearing amide-based ligands generated by a deprotonated amide moiety was prepared with the hypotheses that the strong electron-donating ability of the coordinated anionic nitrogen atom and the proton-responsive OH group near the metal center will improve the catalytic activity for CO 2 hydrogenation and formic acid (FA) dehydrogenation. The effects of the modifications of the ligand architecture on the catalytic activity were investigated for CO 2 hydrogenation at ambient conditions (25 °C with 0.1 MPa H 2 /CO 2 (v/v = 1/1)) and under slightly harsher conditions (50 °C with 1.0 MPa H 2 /CO 2 ) in basic aqueous solutions together with deuterium kinetic isotope effects (KIEs) with selected catalysts. Cp*Ir( L12 )(H 2 O)HSO 4 ( L12 = 6-hydroxy- N -phenylpicolinamidate) that has an anionic coordinating N atom and an OH group in the second coordination sphere, exhibits a turnover frequency (TOF) of 198 h –1 based on the initial 1 h of reaction. This TOF which, to the best of our knowledge, is the highest value ever reported under ambient conditions in basic aqueous solutions. However, Cp*Ir( L10 )(H 2 O)HSO 4 ( L10 = (4-hydroxy- N -methylpicolinamidate) performs better in long-term CO 2 hydrogenation (up to a TON of 14 700 with [Ir] = 10 μM after 348 h and the final formate concentration of 0.643 M with [Ir] = 250 μM) at ambient conditions. Further, the catalytic activity for FA dehydrogenation was examined under three different conditions (pH 1.6, 2.3, and 3.5). The Cp*Ir( L12 )(H 2 O)HSO 4 complex in any of these conditions is less active compared to the picolinamidate catalysts without ortho -OH, owing to its instability. The complex without OH group, Cp*Ir( L8 )(H 2 O)HSO 4 ( L8 = N -phenyl-picolinamidate), exhibits a high TOF (up to 118 000 h -1 ) at 60 °C. Theoretical calculations were performed to examine the catalytic mechanism, and a step-by-step mechanism has been proposed for both CO 2 hydrogenation and FA dehydrogenation reactions. Density functional theory calculations of [Cp*Ir( L3 )(H 2 O)]HSO 4 ( L3 = picolinamidate) and the X-ray structure of the [Cp*Ir( L7 )(H)]·H 2 O ( L7 = N -methylpicolinamidate) complex imply a pH-dependent conformational change from N , N coordination to N , O coordination upon lowering the pH of the aqueous solution.

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

Towards a nonperturbative construction of the S-matrix

We present a nonperturbative recipe for directly computing the S-matrix in strongly-coupled QFTs. The method makes use of spectral data obtained in a Hamiltonian framework and can be applied to a wide range of theories, including potentially QCD. We demonstrate the utility of this prescription in the specific example of the 2+1d O(N) model at large N, using energy eigenstates computed with Hamiltonian truncation to reproduce the full 2 → 2 scattering amplitude for arbitrary (complex) center-of-mass energy.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Uranium-Mediated Peroxide Activation and a Precursor toward an Elusive Uranium cis -Dioxo Fleeting Intermediate

The activation of chalcogen–chalcogen bonds using organometallic uranium complexes has been well documented for S–S, Se–Se, and Te–Te bonds. In stark contrast, reports concerning the ability of a uranium complex to activate the O–O bond of an organic peroxide are exceedingly rare. Herein, we describe the peroxide O–O bond cleavage of 9,10-diphenylanthracene-9,10-endoperoxide in nonaqueous media, mediated by a uranium(III) precursor [(( Me,Ad ArO) 3 N)U III (dme)] to generate a stable uranium(V) bis-alkoxide complex, namely, [(( Me,Ad ArO) 3 N)U V (DPAP)]. This reaction proceeds via an isolable, alkoxide-bridged diuranium(IV/IV) species, implying that the oxidative addition occurs in two sequential, single-electron oxidations of the metal center, including rebound of a terminal oxygen radical. Furthermore, this uranium(V) bis-alkoxide can then be reduced with KC 8 to form a uranium(IV) complex, which upon exposure to UV light, in solution, releases 9,10-diphenylanthracene to generate a cyclic uranyl trimer through formal two-electron photooxidation. Analysis of the mechanism of this photochemical oxidation via density functional theory (DFT) calculations indicates that the formation of this uranyl trimer occurs through a fleeting uranium cis-dioxo intermediate. At room temperature, this cis-configured dioxo species rapidly isomerizes to a more stable trans configuration through the release of one of the alkoxide ligands from the complex, which then goes on to form the isolated uranyl trimer complex.

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

Relativistic Density Functional NMR Tensors Analyzed with Spin–free Localized Molecular Orbitals

The implementation of fast relativistic methods based on density functional theory, in conjunction with localized molecular orbital (LMO) based analysis, allows straightforward interpretations of NMR parameters in terms of contributions from core shells, lone pairs, and bonds, for compounds containing elements from across the periodic table. We present a conceptual review of a frequently used LMO analysis of NMR parameters calculated in the presence of spin-orbit interactions and other relativistic effects. An accompanying example focuses on the 15 N shielding in a heavy metal complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Cockpit task management: A preliminary, normative theory

Cockpit task management (CTM) involves the initiation, monitoring, prioritizing, and allocation of resources to concurrent tasks as well as termination of multiple concurrent tasks. As aircrews have more tasks to attend to due to reduced crew sizes and the increased complexity of aircraft and the air transportation system, CTM will become a more critical factor in aviation safety. It is clear that many aviation accidents and incidents can be satisfactorily explained in terms of CTM errors, and it is likely that more accidents induced by poor CTM practice will occur in the future unless the issue is properly addressed. The first step in understanding and facilitating CTM behavior was the development of a preliminary, normative theory of CTM which identifies several important CTM functions. From this theory, some requirements for pilot-vehicle interfaces were developed which are believed to facilitate CTM. A prototype PVI was developed which improves CTM performance and currently, a research program is under way that is aimed at developing a better understanding of CTM and facilitating CTM performance through better equipment and procedures.

Funk, Ken↗
DOE OSTI2021

Navigating Transition-Metal Chemical Space: Artificial Intelligence for First-Principles Design

Conspectus The variability of chemical bonding in open-shell transition-metal complexes not only motivates their study as functional materials and catalysts but also challenges conventional computational modeling tools. Here, tailoring ligand chemistry can alter preferred spin or oxidation states as well as electronic structure properties and reactivity, creating vast regions of chemical space to explore when designing new materials atom by atom. Although first-principles density functional theory (DFT) remains the workhorse of computational chemistry in mechanism deduction and property prediction, it is of limited use here. DFT is both far too computationally costly for widespread exploration of transition-metal chemical space and also prone to inaccuracies that limit its predictive performance for localized d electrons in transition-metal complexes. These challenges starkly contrast with the well-trodden regions of small-organic-molecule chemical space, where the analytical forms of molecular mechanics force fields and semiempirical theories have for decades accelerated the discovery of new molecules, accurate DFT functional performance has been demonstrated, and gold-standard methods from correlated wavefunction theory can predict experimental results to chemical accuracy. The combined promise of transition-metal chemical space exploration and lack of established tools has mandated a distinct approach. In this Account, we outline the path we charted in exploration of transition-metal chemical space starting from the first machine learning (ML) models (i.e., artificial neural network and kernel ridge regression) and representations for the prediction of open-shell transition-metal complex properties. The distinct importance of the immediate coordination environment of the metal center as well as the lack of low-level methods to accurately predict structural properties in this coordination environment first motivated and then benefited from these ML models and representations. Once developed, the recipe for prediction of geometric, spin state, and redox potential properties was straightforwardly extended to a diverse range of other properties, including in catalysis, computational “feasibility”, and the gas separation properties of periodic metal–organic frameworks. Interpretation of selected features most important for model prediction revealed new ways to encapsulate design rules and confirmed that models were robustly mapping essential structure–property relationships. Encountering the special challenge of ensuring that good model performance could generalize to new discovery targets motivated investigation of how to best carry out model uncertainty quantification. Distance-based approaches, whether in model latent space or in carefully engineered feature space, provided intuitive measures of the domain of applicability. With all of these pieces together, ML can be harnessed as an engine to tackle the large-scale exploration of transition-metal chemical space needed to satisfy multiple objectives using efficient global optimization methods. In practical terms, bringing these artificial intelligence tools to bear on the problems of transition-metal chemical space exploration has resulted in ML-model assessments of large, multimillion compound spaces in minutes and validated new design leads in weeks instead of decades.

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

Coordinated Cation Transport in Ti 3 C 2 T x MXene Membranes

Membrane nanofiltration is an attractive strategy for the selective recovery of high-demand metals from wastewater and brine. Effective sieving of ions in aqueous environments will require precise control over membranes’ nanochannel size and chemistry. Ti 3 C 2 T x MXene is an environmentally stable 2D material that can be processed into laminar membranes containing nanoscale interlayer spaces. The MXene interlayer environment depends on the ion species and amount of water intercalated between MXene sheets, and it is the major factor governing permeation and selectivity through MXene membranes. Coordinated ion–ion and ion-interlayer dynamics in the presence of complex mixtures can impact ion permeability and selectivity. Herein, we observe strong competitive effects between different cations (Li + , Na + , and Ca 2+ ) in binary mixtures, resulting in reduced selectivity when compared with single-salt permeability ratios. X-ray diffraction, molecular dynamics, and density functional theory simulations support the conclusion that cations with stronger attraction to MXene flakes can preferentially occupy the MXene nanochannels and hinder other ions via charge or size exclusion. In conclusion, elucidation of ion transport behavior in MXene under complex conditions will allow for more rational design of efficient ion-sieving membranes.

2D Materials↗
DOE OSTI2023

Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 : Insights from First-Principles

The transformations of complex metal oxides in aqueous settings must be studied to form a chemical understanding of how technologically relevant nanomaterials impact the environment upon disposal. Owing to the inherent heterogeneity and structural complexity of the ternary intercalation material Li(Ni x Mn y Co 1-x-y )O 2 (NMC), the mechanisms of chemical processes at the solid–water interfac e are challenging to model. Here, density functional theory (DFT) + solvent ion methodology is used to study the energetics of stepwise release of two surface metals following unique pathways. Further, the study spans different combinations of metal removal and also considers unique patterns of defects formed by modeling the NMC surface in supercells. The approach here also considers the equilibration of the surface with the surroundings between successive metal removals. A key finding is that a second metal removal prefers to proceed at a metal lattice site adjacent to the initial defect, and this is attributed in part to how the resulting slab with two metal vacancies maintains the most antiferromagnetic couplings between the remaining Ni/Mn.

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

17 O NMR Spectroscopy Reveals CO 2 Speciation and Dynamics in Hydroxide-Based Carbon Capture Materials

Carbon dioxide capture technologies are set to play a vital role in mitigating the current climate crisis. Solid-state 17 O NMR spectroscopy can provide key mechanistic insights that are crucial to effective sorbent development. In this work, we present the fundamental aspects and complexities for the study of hydroxide-based CO 2 capture systems by 17 O NMR. We perform static density functional theory (DFT) NMR calculations to assign peaks for general hydroxide CO 2 capture products, finding that 17 O NMR can readily distinguish bicarbonate, carbonate and water species. However, in application to CO 2 binding in two test case hydroxide-functionalised metal-organic frameworks (MOFs) – MFU-4l and KHCO 3 -cyclodextrin-MOF, we find that a dynamic treatment is necessary to obtain agreement between computational and experimental spectra. We therefore introduce a workflow that leverages machine-learning force fields to capture dynamics across multiple chemical exchange regimes, providing a significant improvement on static DFT predictions. In MFU-4l, we parameterise a two-component dynamic motion of the bicarbonate motif involving a rapid carbonyl seesaw motion and intermediate hydroxyl proton hopping. For KHCO 3 -CD-MOF, we combined experimental and modelling approaches to propose a new mixed carbonate-bicarbonate binding mechanism and thus, we open new avenues for the study and modelling of hydroxide-based CO 2 capture materials by 17 O NMR.

NMR spectroscopy↗