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At least 469 records · Page 26

VERITAS : A density-functional theory-based multiband kinetic model for understanding x-ray spectroscopy of dense plasmas

X-ray spectroscopy has long been a powerful diagnostic tool for hot, dilute plasmas, providing insights into plasma conditions by measuring line shifts and broadenings of atomic transitions. The technique critically depends on the accuracy of atomic physics models used to interpret spectroscopic measurements for inferring plasma properties such as free-electron density and temperature. Over the past decades, the atomic and plasma physics communities have developed robust atomic physics models to account for various processes in hot, dilute classical plasmas. While these models have been successful in that regime, their applicability becomes uncertain when interpreting x-ray spectroscopy experiments of above-solid-density plasmas. Given that finite-temperature density-functional theory (DFT) offers a more accurate description of dense plasma environments, we present the development of a DFT-based multi-band kinetic model, VERITAS, designed to improve the interpretation of x-ray spectroscopic measurements in high-density plasmas produced by laser-driven spherical implosions. This work details the VERITAS model and its application to both time-integrated and time-resolved x-ray spectra from implosion experiments on OMEGA. The advantages and limitations of the VERITAS model will also be discussed, along with potential directions for advancing x-ray spectroscopy of dense and superdense plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

X-ray and electron spectroscopy of (photo)electrocatalysts: Understanding activity through electronic structure and adsorbate coverage

Electronic structure plays a critical role in the kinetics of (photo)electrocatalytic reactions. X-ray and electron spectroscopies provide key determinants—electronic structure, surface adsorbate speciation and coverage quantification, valence state, coordination chemistry, etc.—of catalytic activity and selectivity. Here, we provide an introduction to the fundamental physical concepts, capabilities, and limitations of x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and electron energy-loss spectroscopy as well as provide discussions of (photo)electrocatalysis-relevant publications utilizing each of these techniques. Our objective is to provide those new to x-ray and electron spectroscopies with sufficient information to assess which techniques probe desired material parameters, while also providing experts in each of these spectroscopic fields a bridge to view the importance of these spectroscopies to (photo)electrocatalysis research.

Carvalho, Oliver Quinn (ORCID:0000000344205203)↗

Time-Dependent Corrosion Behavior of Aluminum Using Advanced Electrochemical and Characterization Techniques

The time-dependent corrosion behavior of pure aluminum (Al) in a chloride-containing environment was investigated using various electrochemical and characterization techniques for up to 336 h. Transmission electron microscopic and secondary ion mass spectroscopic analysis revealed the continuous dissolution of the surface film over the immersion time. In the meantime, the increasing passive oxide thickness resulted in the surface film resistance enhancement over the immersion time, as indicated by the electrochemical impedance spectroscopic analysis. The electrochemical noise measurements showed an increase in the corrosion kinetics with immersion time until 60 h because of the accelerated localized corrosion in the early stage of immersion. However, an inhibition in corrosion kinetics occurred after longer immersion times due to corrosion product deposition inside the pit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser Spectroscopy of Exotic Atoms and Molecules Containing Octupole-Deformed Nuclei

This project investigated the nuclear, atomic, and molecular structure of exotic atoms and molecules containing actinide isotopes. These short-lived radioactive systems are challenging to produce and study in the laboratory, yet they offer unique opportunities for fundamental science. These nuclei are predicted to exhibit pear-shaped (octupole) deformation, a rare collective nuclear behavior that dramatically enhances their sensitivity to fundamental physics phenomena such as time-reversal- and parity-violating effects. Such enhancements make them ideal probes for exploring open questions in our understanding of the universe such as the origin of the matter–antimatter asymmetry of the universe. To realize these measurements, the project led the development of a new laser spectroscopy experiment at MIT, and later commissioned at the Facility for Rare Isotope Beams (FRIB) at Michigan State University: the Resonance Ionization Spectroscopy Experiment (RISE). RISE combines the spectroscopic precision of collinear laser spectroscopy with the sensitivity of particle-detection techniques, enabling measurements of rare isotopes produced at rates as low as a few ions per second. The beamline was designed, built, and installed, and was successfully commissioned at FRIB during the grant period. RISE is now a permanent capability of the FRIB facility, and has produced several results on the study of rare atoms and molecules for nuclear structure and fundamental symmetries. In parallel with the FRIB program, the project contributed to the first precision laser-spectroscopy measurements of short-lived radioactive molecules. Working with international collaborators at CERN's ISOLDE facility, the team conducted pioneering experiments on radium monofluoride (RaF) and actinium monofluoride (AcF). The results from this work have been published in major journals of science, including Nature, Science, Nature Physics, Nature Communications, and Physical Review Letters. These findings have guided future experiments on the laser cooling of radioactive molecules, opening a new platform for precision tests of fundamental symmetries.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Scanning Probe Microscopy in the Information Age

Scanning probe microscopy (SPM) has brought scientific exploration, visualization, and control to nanoscale. A plethora of measurement approaches and techniques devised around SPM enabled probing structure and functionalities crucial for virtually all areas of science. While high-resolution electron microscopy techniques preceded scanning probes, SPM effectively opened the door to probing the structure–property relationship on length scales spanning 100s of micrometers down to a single atom. As the complexity of the material systems and the scientific questions increased, so too did the SPM techniques. Substantial efforts have been dedicated toward the development of better instrumentation platforms, probes, and novel spectroscopic measurements; however, many opportunities related to data processing and acquisition in SPM are just being realized now. This chapter will describe the recent progress in data-driven SPM by giving a broad overview of the field, the foundation of the scanning tunneling microscope (STM) and the atomic force microscope (AFM), as well as a description behind the operating principles and dynamic modes. A comprehensive overview of the multi-frequency techniques, Band excitation, and general acquisition mode SPM is given, setting the context for the application of big data, machine learning, and artificial intelligence in the field of dynamic SPM.

Collins, Liam↗

The Completed SDSS-IV Extended Baryon Oscillation Spectroscopic Survey: N-body Mock Challenge for Galaxy Clustering Measurements

We develop a series of N-body data challenges, functional to the final analysis of the extended Baryon Oscillation Spectroscopic Survey (eBOSS) Data Release 16 (DR16) galaxy sample. The challenges are primarily based on high-fidelity catalogues constructed from the Outer Rim simulation - a large box size realization (3h(-1) Gpc) characterized by an unprecedented combination of volume and mass resolution, down to 1.85 x 10(9) h(-1)M(circle dot). We generate synthetic galaxy mocks by populating Outer Rim haloes with a variety of halo occupation distribution (HOD) schemes of increasing complexity, spanning different redshift intervals. We then assess the performance of three complementary redshift space distortion (RSD) models in configuration and Fourier space, adopted for the analysis of the complete DR16 eBOSS sample of Luminous Red Galaxies (LRG5). We find all the methods mutually consistent, with comparable systematic errors on the Alcock-Paczynski parameters and the growth of structure, and robust to different HOD prescriptions - thus validating the robustness of the models and the pipelines used for the baryon acoustic oscillation (BAO) and full shape clustering analysis. In particular, all the techniques are able to recover and alpha(11) to within 0.9 per cent, and f sigma(8) to within 1.5 per cent. As a by-product of our work, we are also able to gain interesting insights on the galaxy-halo connection. Our study is relevant for the final eBOSS DR16 'consensus cosmology', as the systematic error budget is informed by testing the results of analyses against these high-resolution mocks. In addition, it is also useful for future large-volume surveys, since similar mock-making techniques and systematic corrections can be readily extended to model for instance the Dark Energy Spectroscopic Instrument (DESI) galaxy sample.

cosmology: theory, large-scale structure of Univer↗

Metal–Organic Framework-Based Microfluidic Impedance Sensor Platform for Ultrasensitive Detection of Perfluorooctanesulfonate

The growing global concerns to public health from human exposure to perfluorooctanesulfonate (PFOS) requires rapid, sensitive, in-situ detection where current, state-of-the-art techniques are yet to adequately meet sensitivity and selectivity standards of the real-world. This work presents, for the first time, a synergistic approach for the targeted affinity-based capture of PFOS using a porous sorbent probe that enhances detection sensitivity by embedding it on a microfluidic conductive platform. This novel sorbent-containing platform functions as an electrochemical sensor to directly measure PFOS concentration through a proportional change in electrical response (increase in impedance). The extremely high surface area and pore volume of mesoporous metal-organic framework (MOF) Cr-MIL-101 is used as the probe for targeted PFOS capture based on the affinity of the chromium center towards both the fluorine tail groups as well as the sulfonate functionalities as demonstrated by spectroscopic (NMR and XPS) and microscopic (TEM) studies. Answering the need for an ultrasensitive PFOS detection technique, we are embedding these MOF capture probes inside a microfluidic channel, sandwiched between interdigitated microelectrodes (IDµE). The nanoporous geometry increases the signal to noise ratio of interdigitated microelectrodes tremendously increasing sensitivity; this in combination with the ability of the capture probes to interact with the PFOS at the molecular level and effectively transduce that response electrochemically has allowed us achieve a PFOS detection limit of 0.5 ng/L, which is unprecedented for in-situ analytical PFOS sensors and even comparable to quantification limits achieved using state-of-the-art ex situ techniques.

36 MATERIALS SCIENCE↗

Dynamics of magnetic evaporative beamline cooling for the preparation of cold atomic beams

The most sensitive direct neutrino mass searches today are based on measurement of the end point of the 𝛽 spectrum of tritium to infer limits on the mass of the unobserved neutrino. To avoid the smearing associated with the distribution of molecular final states in the T-He molecule, the next generation of these experiments will need to employ atomic (T) rather than molecular (T 2 ) tritium sources, at currents of at least 10 15 atoms per second. Following production, atomic T can be trapped in gravitational and/or magnetic bottles for 𝛽 spectrum experiments, if and only if it can first be cooled to millikelvin temperatures. Accomplishing this cooling presents substantial technological challenges. The Project 8 collaboration is developing a technique based on magnetic evaporative cooling along a beamline (MECB) for the purpose of cooling T to feed a magnetogravitational trap that also serves as a cyclotron radiation emission spectroscope. Initial tests of the approach are planned in a pathfinder apparatus using atomic Li. Here, this paper presents a method for analyzing the dynamics of the MECB technique and applies these calculations to the design of systems for cooling and slowing of atomic Li and T. A scheme is outlined that could provide a current of T at the millikelvin temperatures required for the Project 8 neutrino mass search.

atom optics↗

Peak2Patch: High-Fidelity Functional Group Identification through Attention-Based Fusion of Infrared and Mass Spectra

Identifying molecular structure based on spectroscopic readings is a key task in a variety of chemical and biological applications. Common spectroscopy techniques, such as Infrared (IR) Spectroscopy and Mass Spectrometry (MS), provide detailed information on the structure of molecular compounds but nonetheless require expert-level knowledge to decode. Machine learning has emerged as a potential solution for automating structure prediction from chemical spectra; however, current approaches generally focus on single sensor modalities, neglecting to leverage the complementary information contained within differing spectra. In this paper, we introduce Peak2Patch, a novel approach to fusion-enhanced prediction of functional groups from IR and mass spectra. First, we perform a detailed comparison of backbone networks for encoding both sparse mass spectra and dense IR spectra and demonstrate the superior performance of transformer neural networks over current state-of-the-art convolutional neural networks. Second, we evaluate three broad categories of fusion: early (raw feature), middle (deep feature), and late (decision) fusion, demonstrating the potential of a deep feature fusion-based approach. Lastly, we present Peak2Patch, our attention-based fusion scheme, which leverages cross-attention to mix features between encoded tokens of the two modalities. We validate our approach on a publicly available multimodal spectroscopic data set of 790k simulated molecules, demonstrating a large improvement in functional group prediction over both the previous state-of-the-art and our own strong single-modal baselines.

Jacobson, Philip [Sandia National Laboratories (SN↗

Elucidation of Ce/Zr ratio effects on the physical properties and catalytic performance of CuO x /Ce y Zr 1− y O 2 catalysts

Although cerium oxide (CeO 2 ) is widely used as a catalyst support, its limited defect sites and surface oxygen vacancy/mobility should be improved. The incorporation of zirconium (Zr) in the cerium (Ce) lattice is shown to increase the number of oxygen vacancies and improve catalytic activity. Using a fixed surface density (SD) of copper (∼2.3 Cu atoms per nm 2 ) as a surface species, the role of the support (Ce y Zr 1−y O 2 (y = 1.0, 0.9, 0.6, 0.5, and 0.0)) and defect site effects in the CO oxidation reaction was investigated. Spectroscopic (e.g., Raman, XRD, XPS) and microscopic (e.g., SEM-EDX, HR-TEM) characterization techniques were applied to evaluate the defect sites, crystallite size, lattice parameters, chemical composition, oxidation states of elements and microstructure of the catalysts. Here, the CO oxidation reaction with varied CO : O 2 ratios (1 : 5, 1 : 1, and 1 : 0.5 (stoichiometric)) was used as a model reaction to describe the relationship between the structure and the catalytic performance of each catalyst. Based on the characterization results of Ce y Zr 1−y O 2 materials, the addition of Zr causes physical and chemical changes to the overall material. The inclusion of Zr into the structure of CeO 2 decreased the overall lattice parameter of the catalyst and increased the number of defect sites. The prepared catalysts were able to reach complete CO conversion (∼100%) at low temperature conditions (<200 °C), each showing varied reaction activity. The difference in CO oxidation activity was then analyzed and related to the structure, wherein Cu loading, surface oxygen vacancies, reduction–oxidation ability, CuO x –support interaction and oxygen mobility in the catalyst were the crucial descriptors.

36 MATERIALS SCIENCE↗

Phase noise limited frequency shift impulsive Raman spectroscopy

We introduce a method to enable optical amplification of a coherent Raman spectroscopy signal, which we call radio frequency (RF) Doppler Raman spectroscopy. In this article, we consider the perturbation of a probe pulse in a sample due to an excited Raman vibrational coherence as a generalized Doppler shift, which connects a time-varying optical path length (the product of the propagation length and refractive index, OPL = n ℓ) with an optical frequency shift. Amplification of a Raman signal outside of the focused interaction is enabled by converting the Doppler frequency shift experienced by a laser probe pulse into a periodic timing jitter. This transit time perturbation is detected through the phase of a RF electronic signal measured at a harmonic of the probe pulse train with a method adapted from precision metrology techniques used to measure laser pulse train timing jitter. Measurement of a timing jitter allows access to much lower noise floors than other coherent Raman techniques, and by exploiting the new capability to scale the signal of a coherent Raman spectroscopic signal, this method opens the potential to detect very weak Raman signals that are currently not observable due to limits of illumination intensity imposed by laser damage to the specimen and noise.

47 OTHER INSTRUMENTATION↗

Reconstructions from randomly generated longitudinal electron bunch profiles with Gaussian envelopes using the Gerchberg–Saxton algorithm

Knowledge of longitudinal electron bunch profiles is vital to optimize the performance of plasma wakefield accelerators and x-ray free electron laser linacs. Because of their importance to these novel applications, noninvasive frequency domain techniques are often employed to reconstruct longitudinal bunch profiles from coherent synchrotron, transition, or undulator radiation measurements. In this paper, we detail several common reconstruction techniques involving the Kramers–Kronig phase relationship and Gerchberg–Saxton algorithm. Additionally, through statistical analysis, we draw general conclusions about the accuracy of these reconstruction techniques and the most suitable candidate for reconstructing well-isolated longitudinal bunch profiles from spectroscopic data.

47 OTHER INSTRUMENTATION↗

Atomic fluctuations in electronic materials revealed by dephasing

The microscopic origin and timescale of the fluctuations of the energies of electronic states has a significant impact on the properties of interest of electronic materials, with implication in fields ranging from photovoltaic devices to quantum information processing. Spectroscopic investigations of coherent dynamics provide a direct measurement of electronic fluctuations. Modern multidimensional spectroscopy techniques allow the mapping of coherent processes along multiple time or frequency axes and thus allow unprecedented discrimination between different sources of electronic dephasing. Exploiting modern abilities in coherence mapping in both amplitude and phase, we unravel dissipative processes of electronic coherences in the model system of CdSe quantum dots (QDs). The method allows the assignment of the nature of the observed coherence as vibrational or electronic. The expected coherence maps are obtained for the coherent longitudinal optical (LO) phonon, which serves as an internal standard and confirms the sensitivity of the technique. Fast dephasing is observed between the first two exciton states, despite their shared electron state and common environment. This result is contrary to predictions of the standard effective mass model for these materials, in which the exciton levels are strongly correlated through a common size dependence. In contrast, the experiment is in agreement with ab initio molecular dynamics of a single QD. Electronic dephasing in these materials is thus dominated by the realistic electronic structure arising from fluctuations at the atomic level rather than static size distribution. The analysis of electronic dephasing thereby uniquely enables the study of electronic fluctuations in complex materials.

36 MATERIALS SCIENCE↗

Structure of active methyl-CoM reductase, Earth’s main methane producer

Summary Our work reveals the structure of the active state of Methyl-Coenzyme M Reductase (MCR), the key and rate-limiting enzyme in biological methane formation. We find large differences between the active Ni(I) and inactive Ni(II) proteins and provide insight into how nature makes and breaks the C-H bond of methane. The Ni(II)-F430 center in inactive MCR contains four planar nitrogen ligands, a lower axial glutamine oxo, and an upper axial thiolate. The Ni(I)-enzyme replaces the axial ligands with a single water. The one-electron redox change results in movement of the Ni ion and upward swing of the β-lactam ring in the tetrapyrrole coupled to a domino-like protein quake through second sphere residues, inter-subunit interactions, a substrate tunnel, affecting even the dimensions of the unit cell. These structural changes lead Ni(I)-MCR to release a charge clamp that, in the Ni(II) state, locks down substrate Coenzyme B. Determining the Ni(I)-MCR structure required development of rigorous anaerobic crystallographic techniques. Validation of the MCR redox state was accomplished by in-line and parallel spectroscopic and unit cell analyses. This structure has large implications for developing technologies to limit methane emissions and efficiently produce biofuels. Methodology described here will enhance structural biology for other oxygen-sensitive enzymes.

09 BIOMASS FUELS↗

Reduction of spectroscopic overlap across the Z = 8 shell in neutron-rich nuclei

The recent discovery and spectroscopic measurements of 27 O and 28 O suggests the disappearance of the N = 20 shell structure in these neutron-rich oxygen isotopes. We measured one- and two-proton removal cross sections from 27 F and 29 N, respectively, extracting spectroscopic factors and comparing them to shell model overlap functions coupled with eikonal reaction model calculations. The invariant mass technique was used to reconstruct the two-body ( 24 O + n) and three-body ( 24 O + 2n) decay energies from knockout reactions of 27 F (106.2 MeV/u) and 29 Ne (112.8 MeV/u) beams impinging on a 9 Be target. The one-proton removal from 27 F strongly populated the ground state of 26 O and the extracted cross section of $3.4^{+0.3}_{-1.5}$ mb agrees with eikonal model calculations that are normalized by the shell model spectroscopic factors and account for the systematic reduction factor observed for single nucleon removal reactions within the models used. For the two-proton removal reaction from 29 Ne an upper limit of 0.08 mb was extracted for populating states in 27 O decaying though the ground state of 26 O. The measured upper limit for the population of the ground state of 26 O in the two-proton removal reaction from 29 Ne indicates a significant difference in the underlying nuclear structure of 27 F and 29 Ne.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Velocity reconstruction in the era of DESI and Rubin/LSST. II. Realistic samples on the light cone

Reconstructing the galaxy peculiar velocity field from the distribution of large-scale structure plays an important role in cosmology. On one hand, it gives us an insight into structure formation and gravity; on the other, it allows us to selectively extract the kinetic Sunyaev-Zel’dovich (kSZ) effect from cosmic microwave background maps. In this work, we employ high-accuracy synthetic galaxy catalogs on the light cone to investigate how well we can recover the velocity field when utilizing the three-dimensional spatial distribution of the galaxies in a modern large-scale structure experiment such as the Dark Energy Spectroscopic Instrument (DESI) and the Rubin Observatory Legacy Survey of Space and Time. In particular, we adopt the standard technique used in baryon acoustic oscillation analysis for reconstructing the Zel’dovich displacements of galaxies through the continuity equation, which yields a first-order approximation to their large-scale velocities. We investigate variations in the number density, bias, mask, area, redshift noise, and survey depth, as well as modifications to the settings of the standard reconstruction algorithm. Since our main goal is to provide guidance for planned kSZ analysis between DESI and the Atacama Cosmology Telescope, we apply velocity reconstruction to a faithful representation of DESI spectroscopic and photometric targets. We report the cross-correlation coefficient between the reconstructed and the true velocities along the line of sight. For the DESI Y1 spectroscopic survey, we expect the correlation coefficient to be r ≈ 0.64, while for a photometric survey with δ z /(1+z) = 0.02, as is approximately the case for the Legacy Survey used in the target selection of DESI galaxies, r shrinks by half to r ≈ 0.31. Here, we hope the results in this paper can be used to inform future kSZ stacking studies and other velocity reconstruction analyses planned with the next generation of cosmology experiments.

79 ASTRONOMY AND ASTROPHYSICS↗

Dark Energy Survey Year 3 results: calibration of lens sample redshift distributions using clustering redshifts with BOSS/eBOSS

ABSTRACT We present clustering redshift measurements for Dark Energy Survey (DES) lens sample galaxies used in weak gravitational lensing and galaxy clustering studies. To perform these measurements, we cross-correlate with spectroscopic galaxies from the Baryon Acoustic Oscillation Survey (BOSS) and its extension, eBOSS. We validate our methodology in simulations, including a new technique to calibrate systematic errors that result from the galaxy clustering bias, and we find that our method is generally unbiased in calibrating the mean redshift. We apply our method to the data, and estimate the redshift distribution for 11 different photometrically selected bins. We find general agreement between clustering redshift and photometric redshift estimates, with differences on the inferred mean redshift found to be below |Δz| = 0.01 in most of the bins. We also test a method to calibrate a width parameter for redshift distributions, which we found necessary to use for some of our samples. Our typical uncertainties on the mean redshift ranged from 0.003 to 0.008, while our uncertainties on the width ranged from 4 to 9 per cent. We discuss how these results calibrate the photometric redshift distributions used in companion papers for DES Year 3 results.

79 ASTRONOMY AND ASTROPHYSICS↗

Watching a signaling protein function: What has been learned over four decades of time-resolved studies of photoactive yellow protein

Photoactive yellow protein (PYP) is a signaling protein whose internal p-coumaric acid chromophore undergoes reversible, light-induced trans-to-cis isomerization, which triggers a sequence of structural changes that ultimately lead to a signaling state. Since its discovery nearly 40 years ago, PYP has attracted much interest and has become one of the most extensively studied proteins found in nature. The method of time-resolved crystallography, pioneered by Keith Moffat, has successfully characterized intermediates in the PYP photocycle at near atomic resolution over 12 decades of time down to the sub-picosecond time scale, allowing one to stitch together a movie and literally watch a protein as it functions. But how close to reality is this movie? To address this question, results from numerous complementary time-resolved techniques including x-ray crystallography, x-ray scattering, and spectroscopy are discussed. Emerging from spectroscopic studies is a general consensus that three time constants are required to model the excited state relaxation, with a highly strained ground-state cis intermediate formed in less than 2.4 ps. Persistent strain drives the sequence of structural transitions that ultimately produce the signaling state. Crystal packing forces produce a restoring force that slows somewhat the rates of interconversion between the intermediates. Moreover, the solvent composition surrounding PYP can influence the number and structures of intermediates as well as the rates at which they interconvert. When chloride is present, the PYP photocycle in a crystal closely tracks that in solution, which suggests the epic movie of the PYP photocycle is indeed based in reality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗