Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “atomic spectra”

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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Real-Space Local Dynamics in 1,2,3-Triazole Using Inelastic Neutron Scattering

Enhancing proton transport in polymer electrolytes is crucial for advancing next-generation solid-state batteries, yet our understanding of proton conductivity in nonaqueous environments remains limited due to a lack of atomic-scale insights. Here, in this study, we investigated the atomic-scale dynamics of 1,2,3-triazole, a small molecule capable of dynamic hydrogen bonding, as a model system for proton hopping in nonaqueous environments. Using the real-space correlation function determined by the double Fourier transformation of inelastic neutron scattering spectra, we identified that the self-motion of protons and intermolecular dynamics occur on comparable time scales. Furthermore, we observed that the activation energy associated with the intermolecular dynamics matches the energy barrier for molecular rotations determined through Density Functional Theory calculations. These findings underscore the importance of controlling molecular dynamics at the atomic scale to control proton transport. Additionally, we demonstrated that intermolecular dynamics in systems involving protons can be studied using inelastic neutron scattering even without deuteration, thereby providing a broader avenue for studying atomic-scale dynamics in soft matter systems.

Shinohara, Yuya [Oak Ridge National Laboratory (OR↗
NASA NTRS1987

Product energy distributions and energy partitioning in O atom reactions on surfaces

Surface reactions involving O atoms are likely to be highly exoergic, with different consequences if energy is channeled mostly to product molecules or surface modes. Thus the surface may become a source of excited species which can react elsewhere, or a sink for localized heat deposition which may disrupt the surface. The vibrational energy distribution of the product molecule contains strong clues about the flow of released energy. Two instructive examples of energy partitioning at surfaces are the Pt catalyzed oxidations: (1) C(ads) + O(ads) yields CO* (T is greater than 1000 K); and (2) CO(ads) + O(gas) yields CO2* (T is approx. 300 K). The infrared emission spectra of the excited product molecules were recorded and the vibrational population distributions were determined. In reaction 1, energy appeared to be statistically partitioned between the product CO and several Pt atoms. In reaction 2, partitioning was non-statistical; the CO2 asymmetric stretch distribution was inverted. In gas reactions these results would indicate a long lived and short lived activated complex. The requirement that Pt be heated in O atoms to promote reaction of atomic O and CO at room temperature is specifically addressed. Finally, the fraction of released energy that is deposited in the catalyst is estimated.

Halpern, Bret↗
DOE OSTI2022

Lattice dynamics of high-pressure hydrides studied by inelastic neutron scattering

Due to the small mass and anomalously large neutron scattering cross-section of proton (about 80 barns compared to a few barns for other nuclei), inelastic neutron scattering is considered as one of the most effective tools in studying optical vibrations of hydrogen atoms in metal hydrides. The current review is focused on the binary hydrides of 3d- and 4d-metals of groups VI–VIII, which were produced at high hydrogen pressures of several gigapascals in relatively large quantities of hundreds of mg, quenched to low temperature and studied by INS ex situ at ambient pressure with high statistical accuracy. One of the unusual effects revealed by INS is a strong increase in the strength of the metal-hydrogen interactions with decreasing atomic number of the d-metal accompanied by an increase in the Me-H distance. Based on the available experimental results, the spectra g(E) of the phonon density of states and temperature dependencies CV(T) of the heat capacity at constant volume at T up to 1000 K have been derived in this paper and presented both in the figures and in digital form. This provides the reference data for the theoretical investigations of the crystal structures and compositions of new practically important hydrides giving the opportunity to validate calculation methods by comparing the calculated g(E) and CV(T) with the accurate experimental dependencies for the binary hydrides. Recent INS studies showed [R.A. Klein et al., J. Alloy. Compd. 894 (2022) 162381] that the fingerprints of anomalously short H-H separations of 1.6 Å violating the “2 Å rule” can be easily and unambiguously identified in the complex INS spectra of quaternary hydrides (La,Ce)NiInH 1+x . This makes neutron spectroscopy an attractive means for obtaining valuable data in the search for novel hydrides with a record high hydrogen capacity.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Interpreting the Operando X-ray Absorption Near-Edge Structure of Supported Cu and CuPd Clusters in Conditions of Oxidative Dehydrogenation of Propane: Dynamic Changes in Composition and Size

Supported subnano-cluster catalysts are highly dynamic, developing true active sites only under the pressures and temperatures of reaction conditions. Operando X-ray absorption near-edge structure (XANES) spectroscopy can track changes in the oxidation state and the local environment of cluster atoms, providing insight into the development of these active sites. While bulk metal, oxide, and hydroxide standards are often used for fitting experimental XANES spectra to obtain average oxidation states, we recently showed that computed cluster standards of relevant compositions are a more suitable basis, producing more accurate fits. Here, we theoretically interpret the operando XANES of supported Cu 3 Pd and Cu 4 clusters during temperature-programmed reaction (TPRx) of oxidative dehydrogenation of propane. We use an expanded basis set including both globally optimized computed clusters and bulk standards. Not only can we track reversible composition/oxidation state change with temperature, but also the irreversible growth of the bulk fraction upon heating, which we attribute to cluster sintering. This has important implications for the mechanism of the catalyzed reaction and the nature of the available active sites. Here, we propose that operando XANES provides most significant insight into the nature of supported cluster catalysts in reaction conditions when interpreted using mixed computed cluster and bulk standards.

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

Core-Level Spectroscopy with Hard and Soft X-rays on Phosphorus-Containing Compounds for Energy Conversion and Storage

The electronic properties of nine solid phosphorus (P)-containing compounds with varying oxidation states and chemical environments, including GaP (–III) , InP (–III) , red-P (0) , H 3 P (III) O 3 , Na 2 H 2 P 2 (IV) O 6 , H 3 P (V) O 4 , KH 2 P (V) O 4 , Na 2 HP (V) O 4 , and InP (V) O 4 , are investigated using X-ray absorption near-edge structure (XANES) spectroscopy in the hard (P K-edge) and soft X-ray regime (P L 2,3 - edge). We find shifts in the absorption-edge positions and correlate them with the ligands surrounding the P atom, likely causing a different core–hole interaction screening for different compounds. Complementing the experimental analysis, ab initio many-body calculations of XANES spectra provide insights into the excitonic nature of the observed spectral features and their impact on the electronic structure of the materials. Furthermore, we report on P K-edge XANES measurements on aqueous phosphorus-containing acids, including H 3 PO 3 , H 3 PO 4 , and their mixtures. At first sight, the spectra of the aqueous acids are similar to those of their solid counterparts. However, close inspection reveals a slight red shift of the absorption edge and the presence of fewer spectral features compared with spectra of the respective solids. Mixtures of aqueous acids display spectral features corresponding to the individual components, indicating the potential for speciation and quantification through fingerprinting.

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

A non-local thermodynamic equilibrium, line-blanketed synthetic spectrum of Iota Herculis - C, Al, and Si lines

A non-LTE line-blanketed model stellar atmosphere is used to compute a model of I Herculis (B3 IV) with a Teff of 17,500 K and a log g of 3.75, following the conclusions of Peters and Polidan (1985). Detailed profiles of a number of lines of C, Al, and Si in the 1200-2000-A region are computed, including the resonance lines of C II, Al II, and Al III. These profiles are compared to observations obtained from the coaddition of eight IUE SWP images, using a technique developed by Leckrone and Adelman (1989). Comparison of carbon lines with a model that is underabundant in carbon by a factor of 2 relative to the sun indicates that the C abundance of Iota Her is at most one-half solar. Non-LTE effects are examined by comparing an LTE model possessing identical atmospheric parameters with the non-LTE model. Substantial differences in the populations of the model atomic states are found, but differences in the temperature structure of the two models often mask the non-LTE effects in the synthetic spectra.

Grigsby, James A.↗
NASA NTRS2014

Abiotic Ozone and Oxygen in Atmospheres Similar to Prebiotic Earth

The search for life on planets outside our solar system will use spectroscopic identification of atmospheric biosignatures. The most robust remotely detectable potential biosignature is considered to be the detection of oxygen (O 2 ) or ozone (O 3 ) simultaneous to methane (CH 4 ) at levels indicating fluxes from the planetary surface in excess of those that could be produced abiotically. Here we use an altitude-dependent photochemical model with the enhanced lower boundary conditions necessary to carefully explore abiotic O 2 and O 3 production on lifeless planets with a wide variety of volcanic gas fluxes and stellar energy distributions. On some of these worlds, we predict limited O 2 and O 3 buildup, caused by fast chemical production of these gases. This results in detectable abiotic O 3 and CH 4 features in the UV-visible, but no detectable abiotic O 2 features. Thus, simultaneous detection of O 3 and CH 4 by a UV-visible mission is not a strong biosignature without proper contextual information. Discrimination between biological and abiotic sources of O 2 and O 3 is possible through analysis of the stellar and atmospheric context-particularly redox state and O atom inventory-of the planet in question. Specifically, understanding the spectral characteristics of the star and obtaining a broad wavelength range for planetary spectra should allow more robust identification of false positives for life. This highlights the importance of wide spectral coverage for future exoplanet characterization missions. Specifically, discrimination between true and false positives may require spectral observations that extend into infrared wavelengths and provide contextual information on the planet's atmospheric chemistry.

planets and satellites↗
NASA NTRS1982

X-ray nebular models

Theoretical models are presented for the temperature and ionization structure of spherically symmetric, constant density, gaseous nebulae surrounding compact X-ray sources and for the optical, UV, and X-ray spectra emerging from the nebulae. The structure is determined by assuming a local balance between heating and cooling in the gas, and the radiation field is found by solving a simplified equation of transfer. The calculations include an accurate and comprehensive treatment of the atomic processes affecting the state of the gas and the radiation field. The destruction of line radiation during resonance scattering causes models to be significantly hotter and more highly ionized than previous models of the same type. Model results are presented for a wide variety of gas densities and X-ray source spectra, scaling laws which allow these results to be generalized to a wide variety of astrophysical solutions are discussed, and column densities of multiply charged species are tabulated.

Kallman, T. R.↗
DOE OSTI2021

The Gaia-ESO Survey: Oxygen Abundance in the Galactic Thin and Thick Disks

We analyze the oxygen abundances of a stellar sample representative of the two major Galactic populations: the thin and thick disks. The aim is to investigate the differences between members of the Galactic disks and contribute to the understanding of the origin of oxygen chemical enrichment in the Galaxy. The analysis is based on the [O i] = 6300.30 Å oxygen line in high-resolution spectra (R ∼ 52,500) obtained from the Gaia-ESO public spectroscopic Survey (GES). By comparing the observed spectra with a theoretical data set computed in LTE with the SPECTRUM synthesis and ATLAS12 codes, we derive the oxygen abundances of 516 FGK dwarfs for which we have previously measured carbon abundances. Based on kinematic, chemical, and dynamical considerations, we identify 20 thin and 365 thick disk members. We study the potential trends of both subsamples in terms of their chemistry ([O/H], [O/Fe], [O/Mg], and [C/O] versus [Fe/H] and [Mg/H]), age, and position in the Galaxy. The main results are that (a) [O/H] and [O/Fe] ratios versus [Fe/H] show systematic differences between thin and thick disk stars with an enhanced O abundance of thick disk stars with respect to thin disk members and a monotonic decrement of [O/Fe] with increasing metallicity, even at metal-rich regime; (b) there is a smooth correlation of [O/Mg] with age in both populations, suggesting that this abundance ratio can be a good proxy of stellar ages within the Milky Way; and (c) thin disk members with [Fe/H] ≃ 0 display a [C/O] ratio smaller than the solar value, suggesting a possibly outward migration of the Sun from lower Galactocentric radii.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS2016

Atomic Scattering Factor of the ASTRO-H (Hitomi) SXT Reflector Around the Gold's L Edges

The atomic scattering factor in the energy range of 11.2 - 15.4 keV for the ASTRO-H Soft X-ray Telescope (SXT) is reported. The large effective area of the SXT makes use of photon spectra above 10 keV viable, unlike most other X-ray satellites with total-reflection mirror optics. Presence of gold's L-edges in the energy band is a major issue, as it complicates the function of the effective area. In order to model the area, the reflectivity measurements in the 11.2 - 15.4 keV band with the energy pitch of 0.4 - 0.7 eV were made in the synchrotron beam-line Spring-8 BL01B1. We obtained atomic scattering factors f1 and f2 by the curve fitting to the reflectivities of our witness sample. The edges associated with the L-I, II, and III transitions are identified, of which the depths are found to be roughly 60 shallower than those expected from the Henkes atomic scattering factor.

ASTRO-H Soft X-ray↗
NASA NTRS2014

The Hot Horizontal-Branch Stars in NGC288 - Effects of Diffusion and Stratification on Their Atmospheric Parameters*

Context. NGC288 is a globular cluster with a well developed blue horizontal branch covering the so-called u-jump which indicates the onset of diffusion. It is therefore well suited to study the effects of diffusion in blue horizontal branch (HB) stars. Aims. We compare observed abundances to predictions from stellar evolution models calculated with diffusion and from stratified atmospheric models. We verify the effect of using stratified model spectra to derive atmospheric parameters. In addition we investigate the nature of the overluminous blue HB stars around the u-jump. Methods. We define a new photometric index sz from uvby measurements that is gravity sensitive between 8 000K and 12 000 K. Using medium-resolution spectra and Stroemgren photometry we determine atmospheric parameters (Teff, logg) and abundances for the blue HB stars. We use both homogeneous and stratified model spectra for our spectroscopic analyses. Results. The atmospheric parameters and masses of the hot HB stars in NGC288 show a behaviour seen also in other clusters for temperatures between 9 000K and 14 000 K. Outside this temperature range, however, they follow rather the results found for such stars in (omega)Cen. The abundances derived from our observations are for most elements (except He and P) within the abundance range expected from evolutionary models that include the effects of atomic diffusion and assume a surface mixed mass of 10(exp −7) M. The abundances predicted by stratified model atmospheres are generally significantly more extreme than observed, except for Mg. The use of stratified model spectra to determine effective temperatures, surface gravities and masses moves the hotter stars to a closer agreement with canonical evolutionary predictions. Conclusions. Our results show definite promise towards solving the long-standing issue of surface gravity and mass discrepancies for hot HB stars, but there is still much work needed to arrive at a self-consistent solution.

horizontal branch (HB)↗
DOE OSTI2024

Toward constraint of ionization-potential depression models in a convergent geometry

We demonstrate the value of inner-shell x-ray absorption spectroscopy for dense-plasma atomic physics and explore the coupling between constraint of the thermodynamic state and constraint of ionization-potential depression models. Synthetic K-shell absorption spectra are generated along a radius from a point-like core and analyzed using different ionization-potential depression models. Within this synthetic analysis framework, we identify plasma conditions (T e = 400 eV, ρ = 40g/cm 3 ) accessible by spherical implosions where K-shell absorption spectra discriminate between models if the material temperature is measured to a precision of 20%. The analysis is extensible to a finite-sized core and can be used to guide future studies of ionization-potential depression, informing material and radiative properties of matter in fusion plasmas and stellar interiors.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Ab initio modeling and thermodynamics of hydrated plutonium oxalates

An ab initio study on the plutonium oxalate hydrates: Pu 2 (C 2 O 4 ) 3 ·10H 2 O and Pu(C 2 O 4 ) 2 ·6H 2 O, using PBE exchange-correlation with D3 dispersion correction and Hubbard correction for the plutonium atoms, was performed and compared to experimental vibrational spectral and thermodynamic property values. Here we demonstrated that this technique can accurately predict the experimental infrared spectra Pu(III) oxalate hydrate, as well as the Raman peak of PuO 2 (used to calculate the thermodynamic properties of the oxalates). For Pu(IV) oxalate hydrate we found that our predicted structure agreed qualitatively with PXRD measurements, the only available experimental determination of the structure. Using this method at standard temperature and pressure, we predicted standard enthalpies of formation of -6,755 kJ mol -1 and -3,923 kJ mol -1 and standard Gibbs free energy of formation of -5,899 kJ mol -1 and -3,386 kJ mol -1 for Pu 2 (C 2 O 4 ) 3 ·10H 2 O and Pu(C 2 O 4 ) 2 ·6H 2 O, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Stoichiometry of the Core Determines the Electronic Structure of Core-Shell III-V/II-VI Nanoparticles.

Recently, III-V quantum dots (QDs) emerged as an environmentally friendly alternative to CdSe; however, they exhibit broader emission spectra and inferior photoluminescence quantum yield. Here, we report a computational study of the optoelectronic properties of InxPz and InxGayPz QDs interfaced with zinc chalcogenide shells. Using density functional theory, we show that fine-tuning the composition of the core is critical to achieving narrow emission lines. We show that core-shell nanoparticles, where the core has the same diameter but different stoichiometries, may absorb and emit at different wavelengths, leading to broad absorption and emission spectra. The value of the fundamental gap of the core-shell particles depends on the ratio between the number of group III and P atoms in the core and is maximized for the 1:1 composition. We also show that the interplay between quantum confinement and strain determines the difference in the electronic properties of III-V QDs interfaced with ZnS or ZnSe shells.

Rusishvili, Mariami↗
DOE OSTI2024

Infrared Spectrum of the Pyrene Anion in the CH Stretching Region

In this work, we report the infrared spectrum of pyrene anion, measured using messenger tagging with up to three Ar atoms. We assign the spectrum using density functional theory and vibrational perturbation theory. Additionally, we discuss our results in the context of computed and experimental spectra from the literature as well as recent observations from astronomical sources, addressing the question whether PAH anions could contribute to the strong infrared emission bands at 3.29 μm from carbon- rich regions of space.

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

5f-Shell Covalency in Actinide Complexes

This talk will focus on the theoretical description & analysis of 5f-shell covalency in actinide complexes, as well as the manifestation of this covalency in spectroscopic parameters such as the pre-edge peak energies and intensities in X-ray absorption near-edge structure (XANES) and related types of spectra, or ligand NMR chemical shifts, according to quantum chemical calculations. We are now able to analyze 5f covalency in the context of the participating atomic orbitals, their energies and interactions in a given molecule, and their overlap. A related issue is the assignment of oxidation states. Examples that will be discussed in the talk are [AnCl6](2-) with An = U, Np, Pu, various organometallic complexes with U and Th, and a recently reported ‘berkelocene’ sandwich complex.

Autschbach, Jochen↗