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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Limits of special material detectability fundamental to idealized dual-energy radiographic systems

Analysis of dual-energy radiographic approaches to the detection of “special” material, i.e. contraband, in otherwise innocuous scenes, such as maritime cargo containers encountered at ports of entry, reveals fundamental limitations of data obtained along a single line-of-sight. The basic equations that describe idealized systems are presented and analyzed so as to identify challenges that are only exacerbated by scatter, noise, and measurement uncertainty. In the mono-energetic limit, the instrumentation and measurement methods reduce to a system of linear equations that are simple to treat: it is observed that there exists a threshold for the minimum amount of high-Z material that can be detected unambiguously (without the risk of false positive or false negative indications), even when the background materials are of finite and of well-known variety. The threshold depends on the quality of prior information about the cargo and the selection of probing energies, and can therefore be minimized by good system design practices and measurement procedures, but persists as a general challenge to security operations. In discussion of this result, it is noted that techniques incorporating other prior information, such as the geometry of cargo and potential contraband, along with data from 2D imaging, have far greater potential. For instance, a simple data analysis method capable of differentiating high-Z spheres from those of more common material is presented. This simple example demonstrates that, although simple line-of-sight transmission radiography may suffer fundamental limitations, there remains good cause to be optimistic about the potential for image analysis in radiographic material identification.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Deep Eutectic Solvents: A Review of Fundamentals and Applications

Deep eutectic solvents (DESs) are an emerging class of mixtures characterized by significant depressions in melting points compared to those of the neat constituent components. These green materials are promising for applications as inexpensive ’designer’ solvents exhibiting a host of tunable physicochemical properties. Here, a detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in this class of solvents. Complex hydrogen bonding behavior is postulated as the root cause of their melt-ing point depressions and physicochemical properties; to understand these hydrogen bonded networks, it is imperative to study these systems as dynamic entities using both simulations and experiments. This review emphasizes recent research efforts in order to elucidate the next steps needed to develop a fundamental framework for understanding DESs. It covers recent developments in DES research, frames outstanding scientific questions, and identifies gainful research thrusts that would advance the field towards predictive models and fundamental understanding of these solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

When Do Band Gap Calculations Agree with Experiments in Monolayer-Protected Cu 14 and Au 20 Atomically Precise Nanoclusters? A (TD)-DFT Comparison of HOMO–LUMO, Fundamental, Optical, and Electrochemical Energy Gaps

In view of the tremendous progress in atomically precise metal nanoclusters where electrochemical and optical energetics are routinely supported by computations to establish structure−function correlations, we explore the relationship between different protocols for measuring and computing band gaps of two distinct organic ligand-protected nanoclusters: [Cu 14 H 10 (MBN) 3 (PPh 3 ) 8 ] + and Au 20 (TBBT) 16 . Through UV/visible spectroscopy and differential pulse voltammetry, we measure optical and electrochemical band gaps in those systems. We then compare these experimentally determined gaps to HOMO−LUMO gaps, fundamental gaps, vertical excitation energies, and E o ox − E o red potentials computed using different density functional theory (DFT) or time-dependent DFT (TDDFT) methods. Specifically, in both copper and gold nanoclusters, we test the effect of truncating inert ligands from the model and compare density functionals with varying degrees of Hartree−Fock (HF) exchange from 0 to 50%, range-separated hybrids with a varying long-range tuning parameter, different correlation functionals, basis sets, and (equilibrium and nonequilibrium) continuum solvation models. Despite having different frontier orbital characters (the copper nanocluster has a metal-to-ligand charge transfer character while the gold nanocluster has metal-centered frontier orbitals), both nanoclusters display a similar sensitivity of the HOMO−LUMO gap to the HF exchange that is partially mitigated when computing the fundamental, optical, and electrochemical gaps. Other factors, such as the nature of the correlation functional, basis set, and geometry relaxation, have a considerably smaller effect on computed band gaps in these systems. Overall, this work provides guidelines for factors of varied importance for correlating computed and experimental band gap values.

Chemical calculations↗
DOE OSTI2021

Moving from Fundamental Knowledge of Kinetics and Mechanisms on Surfaces to Prediction of Catalyst Performance in Reactors

Catalysis is defined by kinetics, but after over a century of catalyst development our kinetic and mechanistic knowledge governing real-world catalysis is still severely lacking. This Perspective considers how we can use the precise knowledge available from both theoretical and fundamental experimental techniques to understand and even predict catalytic performance under operational conditions. Here, we describe advances that link fundamental and "real-world" measurements, crucial elements required to successfully recreate a reaction network, and avenues which appear to offer viable routes to success.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Shining a Light on Some Fundamental Research Opportunities in Semiconductor Photoelectrochemistry

Decades of research in semiconductor photoelectrochemistry have yielded a deep understanding of charge transfer, energetics, and stability at solid−liquid interfaces. Theoretical frameworks developed by Gerischer and contemporaries, together with extensive experimental validation, have clarified the key principles affecting the interfacial kinetics and energetics of semiconductor photoelectrodes. Nevertheless, significant opportunities remain for advances in fundamental understanding of semiconductor photoelectrochemistry. Exciting opportunities include exploiting advances in theory, synthesis, and instrumentation to determine the chemical identity and reactivity of surface states; exerting control of band-edge energetics through molecular-level surface modification processes; and systematically improving emerging photoelectrode protection strategies to enable long-term photoelectrode operation under both oxidative and reductive conditions. Advanced morphologies, such as nanowire and microwire arrays, present new pathways to combine efficient light absorption with effective charge collection and catalyst integration. Unique light−matter interactions during photoelectrochemical deposition of p-type semiconductors readily allow preparation at scale of complex 3D morphologies that are difficult, if not impossible, to access by other methods. Continued exploration of these avenues will expand the fundamental understanding of semiconductor−liquid interfaces and could additionally advance the realization of efficient, stable, and scalable systems for solar fuel generation and other emerging photoelectrochemical applications.

Bean, Paul J. L. [California Institute of Technolo↗
DOE OSTI2024

Friends or Foes: Fundamental Principles of Th-Organic Scaffold Chemistry Using Zr-Analogs as a Guide

The fundamental interest in actinide chemistry, particularly for the development of thorium-based materials, is experiencing a renaissance owing to the recent and rapidly growing attention to fuel cycle reactors, radiological daughters for nuclear medicine, and efficient nuclear stockpile development. Herein, we uncover fundamental principles of thorium chemistry on the example of Th-based extended structures such as metal–organic frameworks in comparison with the discrete systems and zirconium extended analogs, demonstrating remarkable over two-and-half-year chemical stability of Th-based frameworks as a function of metal node connectivity, amount of defects, and conformational linker rigidity through comprehensive spectroscopic and crystallographic analysis as well as theoretical modeling. Despite exceptional chemical stability, we report the first example of studies focusing on the reactivity of the most chemically stable Th-based frameworks in comparison with the discrete Th-based systems such as metal–organic complexes and a cage, contrasting multicycle recyclability and selectivity (>97%) of the extended structures in comparison with the molecular compounds. Altogether, the presented work not only establishes the conceptual foundation for evaluating the capabilities of Th-based materials but also represents a milestone for their multifaceted future and foreshadows their potential to shape the next era of actinide chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Analyzing machine learning models to accelerate generation of fundamental materials insights

Abstract Machine learning for materials science envisions the acceleration of basic science research through automated identification of key data relationships to augment human interpretation and gain scientific understanding. A primary role of scientists is extraction of fundamental knowledge from data, and we demonstrate that this extraction can be accelerated using neural networks via analysis of the trained data model itself rather than its application as a prediction tool. Convolutional neural networks excel at modeling complex data relationships in multi-dimensional parameter spaces, such as that mapped by a combinatorial materials science experiment. Measuring a performance metric in a given materials space provides direct information about (locally) optimal materials but not the underlying materials science that gives rise to the variation in performance. By building a model that predicts performance (in this case photoelectrochemical power generation of a solar fuels photoanode) from materials parameters (in this case composition and Raman signal), subsequent analysis of gradients in the trained model reveals key data relationships that are not readily identified by human inspection or traditional statistical analyses. Human interpretation of these key relationships produces the desired fundamental understanding, demonstrating a framework in which machine learning accelerates data interpretation by leveraging the expertize of the human scientist. We also demonstrate the use of neural network gradient analysis to automate prediction of the directions in parameter space, such as the addition of specific alloying elements, that may increase performance by moving beyond the confines of existing data.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A fundamental look at electrocatalytic sulfur reduction reaction

The fundamental kinetics of the electrocatalytic sulfur reduction reaction (SRR), a complex 16-electron conversion process in lithium–sulfur batteries, is so far insufficiently explored. In this study, by directly profiling the activation energies in the multistep SRR, we reveal that the initial reduction of sulfur to the soluble polysulfides is relatively easy owing to the low activation energy, whereas the subsequent conversion of the polysulfides into the insoluble Li 2 S 2 /Li 2 S has a much higher activation energy, contributing to the accumulation of polysulfides and exacerbating the polysulfide shuttling effect. We use heteroatom-doped graphene as a model system to explore electrocatalytic SRR. We show that nitrogen and sulfur dual-doped graphene considerably reduces the activation energy to improve SRR kinetics. Density functional calculations confirm that the doping tunes the p-band centre of the active carbons for an optimal adsorption strength of intermediates and electroactivity. This study establishes electrocatalysis as a promising pathway to tackle the fundamental challenges facing lithium–sulfur batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Planck intermediate results: XXIV. Constraints on variations in fundamental constants*

Any variation in the fundamental physical constants, more particularly in the fine structure constant, α, or in the mass of the electron, me, affects the recombination history of the Universe and cause an imprint on the cosmic microwave background angular power spectra. We demonstrate that the Planck data allow one to improve the constraint on the time variation of the fine structure constant at redshift z ∼ 10 3 by about a factor of 5 compared to WMAP data, as well as to break the degeneracy with the Hubble constant, H 0 . In addition to α, we can set a constraint on the variation in the mass of the electron, me, and in the simultaneous variation of the two constants. We study in detail the degeneracies between fundamental constants and the cosmological parameters, in order to compare the limits obtained from Planck and WMAP and to determine the constraining power gained by including other cosmological probes. We conclude that independent time variations of the fine structure constant and of the mass of the electron are constrained by Planck to Δα/α = (3.6 ± 3.7) × 10 -3 and Δme/me = (4 ± 11) × 10 -3 at the 68% confidence level. We also investigate the possibility of a spatial variation of the fine structure constant. The relative amplitude of a dipolar spatial variation in α (corresponding to a gradient across our Hubble volume) is constrained to be δα/α = (-2.4 ± 3.7) × 10 -2 .

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

Fundamental properties of field emission-driven direct current microdischarges

For half a century, it has been known that the onset of field emission in direct current microdischarges with gap sizes less than 10 {mu}m can lead to breakdown at applied voltages far less than predicted by Paschen's law. It is still unclear how field emission affects other fundamental plasma properties at this scale. In this work, a one-dimensional fluid model is used to predict basic scaling laws for fundamental properties including ion density, electric field due to space charge, and current-voltage relations in the pre-breakdown regime. Computational results are compared with approximate analytic solutions. It is shown that field emission provides an abundance of cathode electrons, which in turn create large ion concentrations through ionizing collisions well before Paschen's criterion for breakdown is met. Breakdown due to ion-enhanced field emission occurs when the electric field due to space charge becomes comparable to the applied electric field. Simple scaling analysis of the 1D Poisson equation demonstrates that an ion density of n{sub +} Almost-Equal-To 0.1V{sub A}{epsilon}{sub 0}/qd{sup 2} is necessary to significantly distort the electric field. Defining breakdown in terms of this critical ion density leads analytically to a simple, effective secondary emission coefficient {gamma}{sup Prime} of the same mathematical form initially suggested by Boyle and Kisliuk [Phys. Rev. 97, 255 (1955)].

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Fourier transform infrared identification of the ν{sub 5}(σ{sub u}) fundamental of SiC{sub 5}Si

The Fourier transform infrared spectrum of SiC{sub 5}Si was observed by trapping the vapor from the Nd:YAG laser ablation of sintered Si/C rods in solid Ar at ∼20 K. Measurements of {sup 13}C and {sup 29,30}Si isotopic shifts have enabled the identification of the ν{sub 5}(σ{sub u}) vibrational fundamental of the linear isomer of SiC{sub 5}Si at 1590.8 ± 0.2 cm{sup −1}. The results are in excellent agreement with the predictions of density functional theory calculations at the B3LYP/cc-pVDZ level. A second fundamental, ν{sub 4}(σ{sub u}), can only be tentatively identified at 2021.0 cm{sup −1}, because its isotopic shifts are overlapped by absorptions from other species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Communication: Fitting potential energy surfaces with fundamental invariant neural network

A more flexible neural network (NN) method using the fundamental invariants (FIs) as the input vector is proposed in the construction of potential energy surfaces for molecular systems involving identical atoms. Mathematically, FIs finitely generate the permutation invariant polynomial (PIP) ring. In combination with NN, fundamental invariant neural network (FI-NN) can approximate any function to arbitrary accuracy. Because FI-NN minimizes the size of input permutation invariant polynomials, it can efficiently reduce the evaluation time of potential energy, in particular for polyatomic systems. In this work, we provide the FIs for all possible molecular systems up to five atoms. Potential energy surfaces for OH{sub 3} and CH{sub 4} were constructed with FI-NN, with the accuracy confirmed by full-dimensional quantum dynamic scattering and bound state calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Fundamental understanding of chemical processes in extreme ultraviolet resist materials

New photoresists are needed to advance extreme ultraviolet (EUV) lithography. The tailored design of efficient photoresists is enabled by a fundamental understanding of EUV induced chemistry. Processes that occur in the resist film after absorption of an EUV photon are discussed, and a new approach to study these processes on a fundamental level is described. The processes of photoabsorption, electron emission, and molecular fragmentation were studied experimentally in the gas-phase on analogs of the monomer units employed in chemically amplified EUV resists. To demonstrate the dependence of the EUV absorption cross section on selective light harvesting substituents, halogenated methylphenols were characterized employing the following techniques. Photoelectron spectroscopy was utilized to investigate kinetic energies and yield of electrons emitted by a molecule. The emission of Auger electrons was detected following photoionization in the case of iodo-methylphenol. Mass-spectrometry was used to deduce the molecular fragmentation pathways following electron emission and atomic relaxation. To gain insight on the interaction of emitted electrons with neutral molecules in a condensed film, the fragmentation pattern of neutral gas-phase molecules, interacting with an electron beam, was studied and observed to be similar to EUV photon fragmentation. Below the ionization threshold, electrons were confirmed to dissociate iodo-methylphenol by resonant electron attachment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Coupling of torsion and OH-stretching in tert -butyl hydroperoxide. II. The OH-stretching fundamental and overtone spectra

We report the vibrational spectra of gas phase tert-butyl hydroperoxide have been recorded in the OH-stretching fundamental and overtone regions (Δv OH = 1–5) at room temperature using conventional Fourier transform infrared (Δv OH = 1–3) and cavity ring-down (Δv OH = 4–5) spectroscopy. In hydroperoxides, the OH-stretching and COOH torsion vibrations are strongly coupled. The double-well nature of the COOH torsion potential leads to tunneling splitting of the energy levels and, combined with the low frequency of the torsional vibration, results in spectra in the OH-stretching regions with multiple vibrational transitions. In each of the OH-stretching regions, both an OH-stretching and a stretch–torsion combination feature are observed, and we show direct evidence for the tunneling splitting in the OH-stretching fundamental region. We have developed two complementary vibrational models to describe the spectra of the OH-stretching regions, a reaction path model and a reduced dimensional local mode model, both of which describe the features of the vibrational spectra well. We also explore the torsional dependence of the OH-stretching transition dipole moment and show that a Franck–Condon treatment fails to capture the intensity in the region of the stretch–torsion combination features. The accuracy of the Franck–Condon treatment of these features improves with increasing Δv OH .

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

Fundamental optical transitions in hexagonal boron nitride epilayers

Fundamental optical transitions in hexagonal boron nitride (h-BN) epilayers grown on sapphire by metal–organic chemical vapor deposition (MOCVD) using triethylboron as the boron precursor have been probed by photoluminescence (PL) emission spectroscopy. The low temperature (10 K) PL spectrum exhibits two groups of emission lines. The first group includes the direct observation of the free exciton and impurity bound exciton (BX) transitions and phonon replicas of the BX transition, whereas the second group is attributed to the direct observation of the band-to-band transition and its associated phonon replicas. The observations of zero-phonon lines of the band-to-band and exciton transitions, which are supposedly forbidden or “dark” in perfect h-BN crystals, result from a relaxed requirement of momentum conservation due to symmetry-breaking in the presence of high concentrations of impurities/defects and strain, which in turn provided more deterministic values of the energy bandgap (E g ), exciton binding energy (E x ), and binding energy of impurity bound excitons (E BX ) in h-BN epilayers. Excitonic parameters of h-BN epilayers grown by MOCVD, carbon-free chemical vapor deposition, and high purity h-BN bulk materials are compared and discussed. The present results, together with available information in the literature, represent a significant improvement in the understanding of the fundamental optical properties and excitonic parameters of h-BN ultrawide bandgap semiconductors.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Fundamental mass-spin-morphology relation of spiral galaxies

This work presents high-precision measurements of the specific baryon angular momentum j {sub b} contained in stars, atomic gas, and molecular gas, out to ≳ 10 scale radii, in 16 nearby spiral galaxies of the THINGS sample. The accuracy of these measurements improves on existing studies by an order of magnitude, leading to the discovery of a strong correlation between the baryon mass M {sub b}, j {sub b}, and the bulge mass fraction β, fitted by β=−(0.34±0.03) lg (j{sub b}M{sub b}{sup −1}/[10{sup −7} kpc km s{sup −1} M{sub ⊙}{sup −1}])−(0.04±0.01) on the full sample range of 0 ≤ β ≲ 0.3 and 10{sup 9} M {sub ☉} < M {sub b} < 10{sup 11} M {sub ☉}. The corresponding relation for the stellar quantities M {sub *} and j {sub *} is identical within the uncertainties. These M-j-β relations likely originate from the proportionality between jM {sup –1} and the surface density of the disk that dictates its stability against (pseudo-)bulge formation. Using a cold dark matter model, we can approximately explain classical scaling relations, such as the fundamental plane of spiral galaxies, the Tully-Fisher relation, and the mass-size relation, in terms of the M-j(-β) relation. These results advocate the use of mass and angular momentum as the most fundamental quantities of spiral galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

A MACHINE-LEARNING METHOD TO INFER FUNDAMENTAL STELLAR PARAMETERS FROM PHOTOMETRIC LIGHT CURVES

A fundamental challenge for wide-field imaging surveys is obtaining follow-up spectroscopic observations: there are >10{sup 9} photometrically cataloged sources, yet modern spectroscopic surveys are limited to ∼few× 10{sup 6} targets. As we approach the Large Synoptic Survey Telescope era, new algorithmic solutions are required to cope with the data deluge. Here we report the development of a machine-learning framework capable of inferring fundamental stellar parameters (T {sub eff}, log g, and [Fe/H]) using photometric-brightness variations and color alone. A training set is constructed from a systematic spectroscopic survey of variables with Hectospec/Multi-Mirror Telescope. In sum, the training set includes ∼9000 spectra, for which stellar parameters are measured using the SEGUE Stellar Parameters Pipeline (SSPP). We employed the random forest algorithm to perform a non-parametric regression that predicts T {sub eff}, log g, and [Fe/H] from photometric time-domain observations. Our final optimized model produces a cross-validated rms error (RMSE) of 165 K, 0.39 dex, and 0.33 dex for T {sub eff}, log g, and [Fe/H], respectively. Examining the subset of sources for which the SSPP measurements are most reliable, the RMSE reduces to 125 K, 0.37 dex, and 0.27 dex, respectively, comparable to what is achievable via low-resolution spectroscopy. For variable stars this represents a ≈12%-20% improvement in RMSE relative to models trained with single-epoch photometric colors. As an application of our method, we estimate stellar parameters for ∼54,000 known variables. We argue that this method may convert photometric time-domain surveys into pseudo-spectrographic engines, enabling the construction of extremely detailed maps of the Milky Way, its structure, and history.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

DISCOVERY OF THE HOST CLUSTER FOR THE FUNDAMENTAL CEPHEID CALIBRATOR ZETA GEMINORUM

New and existing CORAVEL, UBVJHK{sub s} , HST, HIP/Tycho, ARO, KPNO, and DAO observations imply that the fundamental Cepheid calibrator {zeta} Gem is a cluster member. The following parameters were inferred for {zeta} Gem from cluster membership and are tied to new spectral classifications (DAO) established for 26 nearby stars (e.g., HD53588/B7.5IV, HD54692/B9.5IV): E{sub B-V} = 0.02 {+-} 0.02, log {tau} = 7.85 {+-} 0.15, and d = 355 {+-} 15 pc. The mean distance to {zeta} Gem from cluster membership and six recent estimates (e.g., IRSB) is d=363{+-}9({sigma}{sub x}-bar ){+-}26 ({sigma}) pc. The results presented here support the color-excess and HST parallax derived for the Cepheid by Benedict et al. Forthcoming precise proper motions (DASCH) and Chandra/XMM-Newton observations of the broader field may be employed to identify cluster members, bolster the cluster's existence, and provide stronger constraints on the Cepheid's fundamental parameters.

79 ASTRONOMY AND ASTROPHYSICS↗