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DOE OSTI2024

Discovering invariant spatial features in electron energy loss spectroscopy images on the mesoscopic and atomic levels

Over the last two decades, Electron Energy Loss Spectroscopy (EELS) imaging with a scanning transmission electron microscope has emerged as a technique of choice for visualizing complex chemical, electronic, plasmonic, and phononic phenomena in complex materials and structures. The availability of the EELS data necessitates the development of methods to analyze multidimensional data sets with complex spatial and energy structures. Traditionally, the analysis of these data sets has been based on analysis of individual spectra, one at a time, whereas the spatial structure and correlations between individual spatial pixels containing the relevant information of the physics of underpinning processes have generally been ignored and analyzed only via the visualization as 2D maps. Here, we develop a machine learning-based approach and workflows for the analysis of spatial structures in 3D EELS data sets using a combination of dimensionality reduction and multichannel rotationally invariant variational autoencoders. This approach is illustrated for the analysis of both the plasmonic phenomena in a system of nanowires and in the core excitations in functional oxides using low loss and core-loss EELS, respectively. The code developed in this manuscript is open sourced and freely available and provided as a Jupyter notebook for the interested reader.

36 MATERIALS SCIENCE↗

NASA NTRS1990

Digital filtering of plume emission spectra

Fourier transformation and digital filtering techniques were used to separate the superpositioned spectral phenomena observed in the exhaust plumes of liquid propellant rocket engines. Space shuttle main engine (SSME) spectral data were used to show that extraction of spectral lines in the spatial frequency domain does not introduce error, and extraction of the background continuum introduces only minimal error. Error introduced during band extraction could not be quantified due to poor spectrometer resolution. Based on the atomic and molecular species found in the SSME plume, it was determined that spectrometer resolution must be 0.03 nm for SSME plume spectral monitoring.

Madzsar, George C.↗

NASA NTRS1990

Digital filtering of plume emission spectra

Madzsar, George C.↗

DOE OSTI2020

Th 2 O – , Th 2 Au – , and Th 2 AuO 1,2 – Anions: Photoelectron Spectroscopic and Computational Characterization of Energetics and Bonding

The observation and characterization of the anions: Th 2 O – , Th 2 Au – , and Th 2 AuO 1,2 – is reported. These species were studied through a synergetic combination of anion photoelectron spectroscopy and ab initio correlated molecular orbital theory calculations at the CCSD(T) level with large correlation-consistent basis sets. To better understand the energetics and bonding in these anions and their corresponding neutrals, a range of smaller diatomic to tetratomic species were studied computationally. Correlated molecular orbital theory calculations at the CCSD(T) level showed that in most of these cases, there are close-lying anions and neutral clusters with different geometries and spin states and are consistent with the experimentally observed spectra. Thus, comparison of experimentally determined and computationally predicted vertical detachment energies and electron affinities for different optimized geometries and spin states shows excellent agreement to within 0.1 eV. The structures for both the neutrals and anions have a significant ionic component to the bonding because of the large electron affinity of the Au atom and modest ionization potentials for Th 2 , Th 2 O, and Th 2 O 2 . The analysis of the bonding for the Th–Th bonds from the molecular orbitals is consistent with this ionic model. The results show that there is a wide variation in the bond distance from 2.7 to 3.5 Å for the Th–Th bonds all of which are less than twice the atomic radius of Th of 3.6 Å. The bond distances encompass bond orders from 4 to 0. Furthermore, there can be different bond orders for the same bond distance depending on the nature of the ionic bonding suggesting that one may not be able to correlate the bond order with the bond distance in these types of clusters. In addition, the presence of an Au atom may provide a unique probe of the bonding in such clusters because of its ability to accept an electron from clusters with modest ionization potentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions

Alkene ozonolysis generates short-lived Criegee intermediates that are a significant source of hydroxyl (OH) radicals. Here this study demonstrates that roaming of the separating OH radicals can yield alternate hydroxycarbonyl products, thereby reducing the OH yield. Specifically, hydroxybutanone has been detected as a stable product arising from roaming in the unimolecular decay of the methyl-ethyl-substituted Criegee intermediate (MECI) under thermal flow cell conditions. The dynamical features of this novel multistage dissociation plus a roaming unimolecular decay process have also been examined with ab initio kinetics calculations. Experimentally, hydroxybutanone isomers are distinguished from the isomeric MECI by their higher ionization threshold and distinctive photoionization spectra. Moreover, the exponential rise of the hydroxybutanone kinetic time profile matches that for the unimolecular decay of MECI. A weaker methyl vinyl ketone (MVK) photoionization signal is also attributed to OH roaming. Complementary multireference electronic structure calculations have been utilized to map the unimolecular decay pathways for MECI, starting with 1,4 H atom transfer from a methyl or methylene group to the terminal oxygen, followed by roaming of the separating OH and butanonyl radicals in the long-range region of the potential. Roaming via reorientation and the addition of OH to the vinyl group of butanonyl is shown to yield hydroxybutanone, and subsequent C–O elongation and H-transfer can lead to MVK. A comprehensive theoretical kinetic analysis has been conducted to evaluate rate constants and branching yields (ca. 10–11%) for thermal unimolecular decay of MECI to conventional and roaming products under laboratory and atmospheric conditions, consistent with the estimated experimental yield (ca. 7%).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Unnuclear physics: Conformal symmetry in nuclear reactions

Significance Symmetry plays a key role in modern physics as a guiding principle for fundamental theories of nature. We use the nonrelativistic conformal symmetry to predict universal energy spectra of final states in reactions of quantum particles at vastly different length scales. Our work extends Georgi’s “unparticle” proposal to nonrelativistic spin-1/2 fermions in the unitary regime of strong interactions. These systems form so-called unparticles, which behave characteristically different from normal particles. They can be engineered with ultracold atoms and occur naturally in nuclear reactions with multiple neutrons—a situation we dub “unnuclear physics.” We present the general scenario of unnuclear physics, apply it to identify unnuclei in nuclear reactions, and highlight the opportunity to measure unnuclei at radioactive beam facilities.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2025

Vibrational Signatures of Electronic Properties in Renewable-Energy Catalysis

The objective of this research program is to discover and develop new approaches for ab initio computational simulations of molecular motion. Specifically, this program aims to decipher the connection between the underlying electronic structure and the accordant molecular vibrations in reactive ions and radicals for renewable-energy purposes. Recent experimental progress in ion sources and optical spectroscopies has unearthed considerable new inner-sphere detail for these complexes, but the connection between these spectral signatures and mechanistic information often remains elusive, to the continued frustration of experimentalists. For this purpose, new anharmonic vibrational frequency methods, along with a publicly deployed software package, will be developed. Working closely with committed experimental collaborators, this conceptual and computational framework will be used to explain the results of new spectroscopy experiments, focusing specifically on the inner-shell mechanisms of renewable-energy catalysis. The oxidation half of catalytic water-splitting chemistry will be a central focus, along with fundamental studies of the manner in which strong ions and radicals activate solvent as a chemical species. The resulting products of the research program will include openly available software and algorithms for the ab initio simulation of challenging vibrational spectra, as well as critical mechanistic insight into energy-focused catalytic processes that are opaque to other existing analytical techniques.

42 ENGINEERING↗

DOE OSTI2020

Optimization and Prediction of Spectral Response of Metasurfaces Using Artificial Intelligence

Hot-electron generation has been a topic of intense research for decades for numerous applications ranging from photodetection and photochemistry to biosensing. Recently, the technique of hot-electron generation using non-radiative decay of surface plasmons excited by metallic nanoantennas, or meta-atoms, in a metasurface has attracted attention. These metasurfaces can be designed with thicknesses on the order of the hot-electron diffusion length. The plasmonic resonances of these ultrathin metasurfaces can be tailored by changing the shape and size of the meta-atoms. One of the fundamental mechanisms leading to generation of hot-electrons in such systems is optical absorption, therefore, optimization of absorption is a key step in enhancing the performance of any metasurface based hot-electron device. Here we utilized an artificial intelligence-based approach, the genetic algorithm, to optimize absorption spectra of plasmonic metasurfaces. Using genetic algorithm optimization strategies, we designed a polarization insensitive plasmonic metasurface with 90% absorption at 1550 nm that does not require an optically thick ground plane. We fabricated and optically characterized the metasurface and our experimental results agree with simulations. Finally, we present a convolutional neural network that can predict the absorption spectra of metasurfaces never seen by the network, thereby eliminating the need for computationally expensive simulations. Our results suggest a new direction for optimizing hot-electron based photodetectors and sensors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS2005

XMM-Newton X-Ray Observation of Jupiter

Soft X-ray emission has been observed from the disk of both Jupiter and Saturn as well as from the auroral regions of these planets. The low-latitude disk emission as observed by ROSAT, the Chandra X-Ray Observatory, and XMM-Newton appears to be uniformly distributed across the disk and to be correlated with solar activity. These characteristics suggest that the disk x-rays are produced by: (1) the elastic scattering of solar X-rays by atmospheric neutrals and (2) the absorption of solar X-rays in the carbon K-shell followed by fluorescent emission. The carbon atoms are found in methane molecules located below the homopause. In this paper we present the results of calculations of the scattering albedo for soft x-rays. We also show the calculated x-ray intensity for a range of atmospheric abundances for Jupiter and Saturn and for a number of solar irradiance spectra. The model calculations are compared with recent x-ray observations of Jupiter and Saturn. We conclude that the emission of soft x-rays from the disks of Jupiter and Saturn can be largely explained by the scattering and fluorescence of soft x-rays. We suggest that measured x-ray intensities from the disk regions of Jupiter

Waite, J. Hunter↗

NASA NTRS2012

Hydrocarbons on Saturns Satellites: Relationship to Interstellar Dust and the Solar Nebula

To understand the origin and evolution of our Solar System, and the basic components that led to life on Earth, we study interstellar and planetary spectroscopic signatures. The possible relationship of organic material detected in carbonaceous meteorites, interplanetary dust particles (IDPs), comets and the interstellar medium have been the source of speculation over the years as the composition and processes that governed the early solar nebula have been explored to understand the extent to which primitive material survived or became processed. The Cassini VIMS has provided new data relevant to this problem. Three of Saturn's satellites, Phoebe, Iapetus, and Hyperion, are found to have aromatic and aliphatic hydrocarbons on their surfaces. The aromatic hydrocarbon signature (C-H stretching mode at 3.28 micrometers) is proportionally significantly stronger (relative to the aliphatic bands) than that seen in other Solar System bodies (e.g., comets) and materials (Stardust samples, IDPs, meteorites) and the distinctive sub-features of the 3.4 micrometer aliphatic band (CH2 and CH3 groups) are reminiscent of those widely detected throughout the diffuse ISM. Phoebe may be a captured object that originated in the region beyond the present orbit of Neptune, where the solar nebula contained a large fraction of original interstellar ice and dust that was less processed than material closer to the Sun. Debris from Phoebe now resident on Iapetus and Hyperion, as well as o Phoebe itself, thus presents a unique blend of hydrocarbons, amenable to comparisons with interstellar hydrocarbons and other Solar System materials. The dust ring surrounding Saturn, in which Phoebe is embedded, probably originated from a collision with Phoebe. Dust ring particles are the likely source of the organic-bearing materials, and perhaps the recently identified small particles of Fe detected on Saturn's satellites. Lab measurements of the absolute band strengths of representative aliphatic and aromatic molecules, together with measurements from the VIMS data, allow us to calculate the number of C atoms to find the relative abundances of C atoms in the two kinds of organic molecules. The strength of the prominent aromatic C-H stretch band relative to the aliphatic band complex in Phoebe and Iapetus indicates that the relative abundance of aromatic to aliphatic carbon is very large (greater than 200). In contract, the aromatic band is nearly imperceptible in spectra of interplanetary dust particles (IDP), returned samples from comet 91P/Wild 2, insoluable carbonaceous material in most meteorites, and the diffuse interstellar dust (DISM) (although aromatics are known in all these materials-here we consider only the spectroscopic signature)

Cruikshank, D. P.↗

NASA NTRS2020

High-Precision Determination of Oxygen-Kalpha Transition Energy Excludes Incongruent Motion of Interstellar Oxygen

We demonstrate a widely applicable technique to absolutely calibrate the energy scale of x-ray spectra with experimentally well-known and accurately calculable transitions of highly charged ions, allowing us to measure the K-shell Rydberg spectrum of molecular O2 with 8 meV-uncertainty. We reveal a systematic ~450meV shift from previous literature values, and settle an extraordinary discrepancy between astrophysical and laboratory measurements of neutral atomic oxygen, the latter being calibrated against the aforementioned O2 literature values. Because of the widespread use of such, now deprecated, references, our method impacts on many branches of x-ray absorption spectroscopy. Moreover, it potentially reduces absolute uncertainties there to below the meV level.

M A Leutenegger↗

NASA NTRS1979

Many-electron aspects of molecular promotion in ion-atom collisions - Production of core-excited states of Li in Li/+/-He collisions

Production of core-excited autoionizing states of neutral Li having configurations of the form 1snln(prime)l(prime) has been observed over the impact-energy range from 10-50 keV. Although the results for production of all such states is remarkably consistent with a quasi-molecular-excitation model proposed by Stolterfoht and Leithaeuser (1976), production of individual lines in the observed spectra exhibits collision-velocity dependencies indicative of considerably more complex processes, including processes which appear to be inherently two-electron in nature. Excitation functions are presented for (1s2s/2/)/2/S, 1s(2s2p/3/P)/2/P, 1s(2s2p/1/P)/2/P, and (1s2p/2/)/2/D core-excited state of Li and for total core excitation.

Elston, S. B.↗

DOE OSTI2026

Crystal Orientation Independent Strong TERS Response in Anisotropic ReS2 on Gold

Rhenium disulfide (ReS2) crystallizes in a distorted 1T' lattice with triclinic symmetry arising from Re–Re dimerization, which produces in-plane anisotropic properties and a dense set of Raman-active modes with mixed atomic displacements. Unlike far-field Raman spectroscopy, which shows strong polarization and orientation dependence, tip-enhanced Raman spectroscopy (TERS) probes out-of-plane Raman tensor components. Here we use 785 nm (1.58 eV) gap-mode TERS to investigate monolayer to four-layer thick ReS2 crystals.. TERS maps and averaged spectra reveal that all modes remain invariant under 90° rotation of the crystal, and the only thickness-dependent feature is the emergence of the multilayer breathing mode. These results demonstrate that TERS yields a crystal-orientation-independent Raman response in ReS2 and provides direct access to Raman tensor components that are not easily accessible in conventional far-field measurements.

Valencia Acuna, Pavel A.↗

DOE OSTI2025

Formation and optical properties of indium nanoparticle arrays for deep-UV plasmonics

We utilize a combined computational-experimental approach to examine the influence of indium nanoparticle (NP) array distributions on deep-ultraviolet (UV) plasmon resonances. For photon energies < 5.7 eV, analysis of ellipsometric spectra reveals an increase in silicon reflectance induced by indium NP arrays on silicon. For various energies in the range 5.7–7.0 eV, a decrease in reflectance is induced by the NP arrays. Similar trends in reflectance are predicted from finite-difference time-domain (FDTD) simulations using NP size distributions extracted from atomic-force micrographs as input. In addition, in the energy range of 7.4–9.2 eV, the FDTD simulations reveal reflectance minima, characteristic of localized surface plasmon resonances. Here, electron energy-loss spectroscopy collected from individual indium NPs reveals the presence of LSPR at ≈ 8 eV, further supporting the promise of indium NP arrays on silicon for deep-UV plasmonics.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Irreversible oxygen poisoning: Modeling the initial water dissociation kinetics on δ-Pu(111) and δ-Pu(100) through density functional theory

In this work, the initial kinetics of water dissociation on two facets of δ-plutonium, δ-Pu(111) and δ-Pu(100), are explored through density functional theory in order to understand how water dissociation occurs on these facets. We explored the dissociation of water via the formation of hydroxyls, atomic hydrogen, and atomic oxygen species on each facet. We calculate low energetic barriers for water to split to adsorbed hydrogen and hydroxyl species at 0.19 eV for δ-Pu(111) and 0.07 eV for δ-Pu(100). The hydroxyl has a barrier of 0.64 and 0.37 eV to cleave the hydrogen–oxygen bond on δ-Pu(111) and δ-Pu(100), respectively. Due to the highly exergonic adsorption free energy of atomic oxygen of −2.10 eV, the metallic surfaces are found to be fully covered in oxygen, even with the inclusion of oxygen lateral interactions. When combined with the reaction thermodynamics, this free energy of adsorption forms a molecular oxygen desorption barrier greater than 9.51 eV (918 kJ/mol). These results, combined with simulated temperature programed desorption spectra, indicate that oxygen formed via water dissociation on δ-Pu (111) and (100) facets induces an irreversible poison that prevents further reaction of water directly on metallic plutonium surfaces, most likely due to the strong hybridization of the Pu and O valence states. Therefore, these results imply that another mechanism is responsible for the continuously experimentally measured water dissociation, which is most likely due to the Pu oxide.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Advancements in Validation of TSLs through Inelastic Neutron Scattering and Transmission Measurements [Slides]

This presentation finds that INS measurements are not as variable based on sample composition, because phonon spectra is a properly of the bulk material. Additionally, INS and transmission measurements are and should be the most significant part of TSL validation, as they are the fundamental quantities used by Monte Carlo neutronics codes. Relaying solely on theoretical atomistic calculations for TSL evaluation is not enough, they are highly dependent on inter-atomic potentials (which are not the most accurate depending on the quantity trying to be reproduced) and evaluators knowledge and understanding of the material being studied. When dealing with Crit. benchmarks - While extremely useful for validation of nuclear data at all energies, critical benchmarks are not the best tool to provide a definitive answer on conflicting TSLs. Finally, INS and transmission measurements need to be the basis of validation of TSLs.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS1976

Ultraviolet absorption lines associated with the Vela supernova remnant

Two stars behind the Vela supernova remnant and two stars offset from the remnant have been observed with the UV spectrometer aboard the Copernicus satellite. Over 200 interstellar atomic and molecular absorption features between 1000 and 1400 A have been identified and measured for radial velocity and equivalent width. In many cases, additional information was obtained by studying the detailed shapes of the recorded profiles. Most of the stars show several absorption components, with clouds of the highest radial velocity appearing in the spectra of stars behind the remnant. For each component, column densities were derived using velocity dispersion parameters which yielded the most self-consistent results. Qualitatively, the gas toward the remnant exhibits a number of unusual properties, when compared with normal interstellar material. First, abnormally high radial velocities were evident. Second, the degree of ionization of some elements suggested the existence of ionizing processes significantly more potent than those found in general regions of space. Finally, an investigation of electron densities shows that much of the gas, especially that at high velocity, must exist in the form of relatively thin sheets or filaments. If cosmic abundances prevail, the column densities of high-velocity excited material suggest that H-alpha emission measures could be as large as 100 sq cm/cu pc.

Jenkins, E. B.↗

NASA NTRS2005

Using Beta Cen to Probe the Photosphere-Wind Connection to B Stars

The goal of the project was to probe the connection between the photospheric pulsations and the X-ray production in the stellar winds of B stars. The B1 III star Beta Centauri is a Beta Cephei variable with a high X-ray count rate, and was observed by XMM. Analysis of XMM X-ray spectra showed characteristic plasma temperatures of 0.1, 0.2 and 0.6 keV. Analysis of He-like forbidden-to-intercombination lines was performed to determine the dominant locations of the X-ray emission. At Prism, work focused on developing and upgrading spectral models to calculate forbidden-to-intercombination line ratios using more detailed atomic models than the simple models typically used in the analysis of X-ray spectral lines, thereby allowing us to assess the effects of a broader variety of populating and depopulating channels for energy levels contributing to the observed X-ray line emission. Based on Ne IX lines, the source location was determined to be no farther than 4 stellar radii. Examination of the time variability of the XMM data for Beta Cen showed no significant correlation with the known optical pulsation period for the star, and also did not find any significant periods of variation at X-ray wavelengths.

MacFarlane, Joseph J.↗