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NASA NTRS2011

Frame-Transfer Gating Raman Spectroscopy for Time-Resolved Multiscalar Combustion Diagnostics

Accurate experimental measurement of spatially and temporally resolved variations in chemical composition (species concentrations) and temperature in turbulent flames is vital for characterizing the complex phenomena occurring in most practical combustion systems. These diagnostic measurements are called multiscalar because they are capable of acquiring multiple scalar quantities simultaneously. Multiscalar diagnostics also play a critical role in the area of computational code validation. In order to improve the design of combustion devices, computational codes for modeling turbulent combustion are often used to speed up and optimize the development process. The experimental validation of these codes is a critical step in accepting their predictions for engine performance in the absence of cost-prohibitive testing. One of the most critical aspects of setting up a time-resolved stimulated Raman scattering (SRS) diagnostic system is the temporal optical gating scheme. A short optical gate is necessary in order for weak SRS signals to be detected with a good signal- to-noise ratio (SNR) in the presence of strong background optical emissions. This time-synchronized optical gating is a classical problem even to other spectroscopic techniques such as laser-induced fluorescence (LIF) or laser-induced breakdown spectroscopy (LIBS). Traditionally, experimenters have had basically two options for gating: (1) an electronic means of gating using an image intensifier before the charge-coupled-device (CCD), or (2) a mechanical optical shutter (a rotary chopper/mechanical shutter combination). A new diagnostic technology has been developed at the NASA Glenn Research Center that utilizes a frame-transfer CCD sensor, in conjunction with a pulsed laser and multiplex optical fiber collection, to realize time-resolved Raman spectroscopy of turbulent flames that is free from optical background noise (interference). The technology permits not only shorter temporal optical gating (down to <1 s, in principle), but also higher optical throughput, thus resulting in a substantial increase in measurement SNR.

Nguyen, Quang-Viet↗

DOE OSTI2021

Constraining the baryon abundance with the kinematic Sunyaev-Zel’dovich effect: Projected-field detection using Planck , WMAP , and unWISE

The kinematic Sunyaev-Zel'dovich (kSZ) effect -- the Doppler boosting of cosmic microwave background (CMB) photons scattering off free electrons with non-zero line-of-sight velocity -- is an excellent probe of the distribution of baryons in the Universe. In this paper, we measure the kSZ effect due to ionized gas traced by infrared-selected galaxies from the \emph{unWISE} catalog. We employ the "projected-field" kSZ estimator, which does not require spectroscopic galaxy redshifts. To suppress non-kSZ foreground signals associated with the galaxies (e.g., dust emission and thermal SZ), this estimator requires cleaned CMB maps, which we obtain from \emph{Planck} and \emph{WMAP} data. Using a new "asymmetric" estimator that combines different foreground-cleaned CMB maps to maximize the signal-to-noise, we measure the kSZ$^2$-galaxy cross-power spectrum for three subsamples of the \emph{unWISE} galaxy catalog, which peak at mean redshifts $z \approx$ 0.6, 1.1, and 1.5, have average halo mass $\sim 1$-$5\times 10^{13}$ $h^{-1} M_{\odot}$, and in total contain over 500 million galaxies. After marginalizing over CMB lensing contributions, we measure the amplitude of the kSZ signal $A_{\rm kSZ^2} = 0.42 \pm 0.31$, $5.02 \pm 1.01$, and $8.23 \pm 3.23$, for the three subsamples, where $A_{\rm kSZ^2} = 1$ corresponds to our fiducial model. The combined kSZ detection S/N $>$ 5. We discuss possible explanations for the excess kSZ signal associated with the $z \approx 1.1$ sample, and show that foreground contamination in the CMB maps is very unlikely to be the cause. Our measurements illustrate clearly that no baryons are missing on large scales at low redshifts.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2021

2D Mg-Cu Intermetallic Compounds with Nontrivial Band Topology and Dirac Nodal Lines

Synthesis of vertical heterostructures that include atomically thin layers of materials with topologically nontrivial energy bands is desirable for exploring exotic quantum states. In this study, the authors report on atomic-layer-by-layer deposition of magnesium on copper(111) surface by molecular beam epitaxy, monitored in situ by low-energy electron microscopy and diffraction, and modeled by ab initio theory. It is found that a 2D MgCu 2 intermetallic compound forms during initial Mg deposition and persists till a full monolayer of Mg is formed. Deposition of additional Mg triggers a phase transition from the commensurate MgCu 2 to an incommensurate Mg 2 Cu layer and enables growth of the second layer of Mg. Ab initio calculations indicate non-trivial topology of the electron bands in the interfacial Mg 2 Cu layer and the existence of Dirac nodal lines near the Fermi level. The new 2D Mg 2 Cu material emerges as a promising platform to study new topological states of matter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Control Oriented Models for Co-Design: Technical Overview of MT HVDC, MVDC, and Solid State Transformer Building Blocks

The electric power system is shifting toward a power electronics–enabled grid, where converter based “building blocks” (e.g., high voltage direct current (HVDC) links, multi terminal HVDC (MT HVDC) networks, medium voltage DC (MVDC) links, and solid state transformers (SSTs)) provide fast, precise control of power flows, voltage, and frequency. This report develops and applies publicly shareable electromagnetic transient (EMT) and phasor models to examine how such building blocks can be composed and coordinated to support offshore wind integration, inter area transfers, feeder support, and resilience. Section 2 documents a modular multilevel converter (MMC)–based MT HVDC modeling framework and two use cases: a compact WSCC/IEEE 9 bus test system and a 240 bus “mini WECC” case with five offshore wind plants (OWFs). Phasor to EMT transfer, initialization, and sanity checks are summarized, and neutral demonstrations of normal and contingency operation are reported. Section 3 frames the problem of wind plant inertial frequency response (IFR): shaping energy release and recovery to improve nadir while avoiding aerodynamic stall; representative simulations illustrate the issues without disclosing proprietary control. Section 4 develops MVDC concepts through an IEEE 16 bus loop and an Olympic Peninsula case study that compares AC vs. MVDC corridors and shows how feeder headroom can be pooled via DC couplers. Section 5 surveys SST architectures and identifies a gap: scalable, communication free coordination of multiple SSTs for islanded feeder networks. Across the report, novel methods and configurations under separate publication and IP review are not disclosed; only topic oriented, replicable setups and non proprietary results are shown. These models and use cases are intended as foundations for future publications and co design studies on architecture, control, and coordination of PE enabled grids.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2025

Heterogeneous fatigue damage in a nickel-based single-crystal superalloy unraveled using correlative 3D X-ray technology

Nickel-based single-crystal (Ni-SX) superalloys under cyclic stress are susceptible to cracking at stress-concentration sites, eventually leading to low-cycle fatigue (LCF) failure. LCF cracks typically originate from intrinsic defects (e.g., voids and carbides) within solidified dendrites. However, systematic quantitative experimental analyses of defect-mediated local damage remain limited. To thoroughly understand the microscopic origins and evolution of LCF damage, correlated 3D mapping of dendrites across various regions is essential. Here, in this study, macroscale micro-computed tomography (μ-CT) was initially used to capture internal interdendritic secondary cracks within bulk DD413 superalloy after LCF testing at 760 °C. Subsequently, a multimodal methodology combining synchrotron 3D microdiffraction (3D-μXRD), high-resolution μ-CT, and electron microscopy was established. This approach allowed precise localization of internal damage zones near interdendritic secondary cracks and detailed mapping of the 3D correlated distributions of dendrites, defects, and residual stress/strain fields within these zones at submicron spatial resolution. Finally, the same approach was applied to specimens subjected to interrupted loading at approximately 40 % of the fatigue life to uncover the early damage states of dendrites. The dendrite cores (DCs) and interdendritic regions (IDs) exhibit microscale heterogeneous mechanical responses: nearly defect-free DCs accumulate local irreversible slip along specific slip systems to generate slip bands, while the IDs containing various defects accommodate local microplasticity through the activation of multiple slip systems around these defects. The local tensile stress near defects in the IDs exceeds that in the DC slip band regions by more than threefold, leading to the generation of local damage zones within the IDs. Chain-like defect distributions facilitate the interconnection of these local zones into a continuous damage region, further elevating the overall tensile stress in the IDs. Additionally, geometrically necessary dislocations alone are insufficient as indicators of LCF damage; both the internal stress state and its magnitude must be considered. These experimental results provide critical data and insights for the development of multi-physics fatigue models.

Localized deformation↗

DOE OSTI2022

Influence of the Molecular Structure on the Electrocatalytic Hydrogenation of Carbonyl Groups and H 2 Evolution on Pd

We investigated the electrocatalytic hydrogenation (ECH) of model aldehydes and ketones over carbon supported Pd in aqueous phase. We propose reaction mechanisms based on kinetic measurements and on spectroscopic and electrochemical characterization of the working catalyst. The reaction rates of ECH and of the H 2 evolution reaction (HER) vary with the applied electric potential following trends that strongly depend on the organic substrate. The intrinsic rates of hydrogenation and H 2 evolution are influenced, in opposing ways, by the sorption of the reacting organic substrate. Strong interactions, i.e., higher standard free energies of adsorption of the organic compound, induce high hydrogenation rates but decrease the overall currents. The fast hydrogenation kinetics produces a hydrogen-depleted environment that kinetically hinders the HER and the bulk phase transition of Pd to a H-rich bulk Pd hydride, which is triggered by the applied potential in the absence of reacting organic compounds. As consequence of strong organic-metal interactions, hydrogenation dominates at low overpotential. However, the coverages of organic substrates on the metal surface decrease and the rates of H 2 evolution surpass those of hydrogenation with increasingly negative electric potential. We determined the range of electric potential favoring hydrogenation on Pd and quantitatively deconvoluted the effects of the sorption of the organic compound, and of the rates of proton coupled electron transfers, on the kinetics of both ECH and HER. The results indicate that electrocatalysis offers hydrogenation pathways for polar molecules that are different and, in some cases, faster than those dominating in the absence of an external electric potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Influence of solution phase environmental heterogeneity and fluctuations on vibronic spectra: Perylene diimide molecular chromophore complexes in solution

Ensembles of ab initio parameterized Frenkel-exciton model Hamiltonians for different perylene diimide dimer systems are used, together with various dissipative quantum dynamics approaches, to study the influence of the solvation environment and fluctuations in chromophore relative orientation and packing on the vibronic spectra of two different dimer systems: a π-stacked dimer in aqueous solution in which the relative chromophore geometry is strongly confined by a phosphate bridge and a side-by-side dimer in dichloromethane involving a more flexible alkyne bridge that allows quasi-free rotation of the chromophores relative to one another. These entirely first-principles calculations are found to accurately reproduce the main features of the experimental absorption spectra, providing a detailed mechanistic understanding of how the structural fluctuations and environmental interactions influence the vibronic dynamics and spectroscopy of solutions of these multi-chromophore complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Randomized Algorithms for Scientific Computing (RASC)

Randomized algorithms have propelled advances in artificial intelligence (AI) and represent a foundational research area in advancing AI for Science. Future advancements in DOE Office of Science priority areas such as climate science, astrophysics, fusion, advanced materials, combustion, and quantum computing all require randomized algorithms for surmounting challenges of complexity, robustness, and scalability. Advances in data collection and numerical simulation have changed the dynamics of scientific research and motivate the need for randomized algorithms. For instance, advances in imaging technologies such as X-ray ptychography, electron microscopy, electron energy loss spectroscopy, or adaptive optics lattice light-sheet microscopy collect hyperspectral imaging and scattering data in terabytes, at breakneck speed enabled by state-of-the-art detectors. The data collection is exceptionally fast compared with its analysis. Likewise, advances in high-performance architectures have made exascale computing a reality and changed the economies of scientific computing in the process. Floating-point operations that create data are essentially free in comparison with data movement. Thus far, most approaches have focused on creating faster hardware. Ironically, this faster hardware has exacerbated the problem by making data still easier to create. Under such an onslaught, scientists often resort to heuristic deterministic sampling schemes (e.g., low-precision arithmetic, sampling every nth element) and sacrifice potentially valuable accuracy. Dramatically better results can be achieved via randomized algorithms, reducing the data size as much as or more than naive deterministic subsampling can achieve, while retaining the high accuracy of computing on the full data set. By randomized algorithms we mean those algorithms that employ some form of randomness in internal algorithmic decisions to accelerate time to solution, increase scalability, or improve reliability. Examples include matrix sketching for solving large-scale least-squares problems (see Figure 1) and stochastic gradient descent for training machine learning models. We are not recommending heuristic methods but rather randomized algorithms that have certificates of correctness and probabilistic guarantees of optimality and near-optimality. Such approaches can be useful beyond acceleration, for example, in understanding how to avoid measure zero worst-case scenarios that plague methods such as QR matrix factorization.

97 MATHEMATICS AND COMPUTING↗

NASA NTRS1992

STELAR: An experiment in the electronic distribution of astronomical literature

STELAR (Study of Electronic Literature for Astronomical Research) is a Goddard-based project designed to test methods of delivering technical literature in machine readable form. To that end, we have scanned a five year span of the ApJ, ApJ Supp, AJ and PASP, and have obtained abstracts for eight leading academic journals from NASA/STI CASI, which also makes these abstracts available through the NASA RECON system. We have also obtained machine readable versions of some journal volumes from the publishers, although in many instances, the final typeset versions are no longer available. The fundamental data object for the STELAR database is the article, a collection of items associated with a scientific paper - abstract, scanned pages (in a variety of formats), figures, OCR extractions, forward and backward references, errata and versions of the paper in various formats (e.g., TEX, SGML, PostScript, DVI). Articles are uniquely referenced in the database by journal name, volume number and page number. The selection and delivery of articles is accomplished through the WAIS (Wide Area Information Server) client/server models requiring only an Internet connection. Modest modifications to the server code have made it capable of delivering the multiple data types required by STELAR. WAIS is a platform independent and fully open multi-disciplinary delivery system, originally developed by Thinking Machines Corp. and made available free of charge. It is based on the ISO Z39.50 standard communications protocol. WAIS servers run under both UNIX and VMS. WAIS clients run on a wide variety of machines, from UNIX-based Xwindows systems to MS-DOS and macintosh microcomputers. The WAIS system includes full-test indexing and searching of documents, network interface and easy access to a variety of document viewers. ASCII versions of the CASI abstracts have been formatted for display and the full test of the abstracts has been indexed. The entire WAIS database of abstracts is now available for use by the astronomical community. Enhancements of the search and retrieval system are under investigation to include specialized searches (by reference, author or keyword, as opposed to full test searches), improved handling of word stems, improvements in relevancy criteria and other retrieval techniques, such as factor spaces. The STELAR project has been assisted by the full cooperation of the AAS, the ASP, the publishers of the academic journals, librarians from GSFC, NRAO and STScI, the Library of Congress, and the University of North Carolina at Chapel Hill.

Warnock, A.↗

DOE OSTI2021

Local and long-range atomic/magnetic structure of non-stoichiometric spinel iron oxide nanocrystallites

Spinel iron oxide nanoparticles of different mean sizes in the range 10–25 nm have been prepared by surfactant-free up-scalable near- and super-critical hydrothermal synthesis pathways and characterized using a wide range of advanced structural characterization methods to provide a highly detailed structural description. The atomic structure is examined by combined Rietveld analysis of synchrotron powder X-ray diffraction (PXRD) data and time-of-flight neutron powder-diffraction (NPD) data. The local atomic ordering is further analysed by pair distribution function (PDF) analysis of both X-ray and neutron total-scattering data. It is observed that a non-stoichiometric structural model based on a tetragonal γ-Fe 2 O 3 phase with vacancy ordering in the structure (space group P 4 3 2 1 2) yields the best fit to the PXRD and total-scattering data. Detailed peak-profile analysis reveals a shorter coherence length for the superstructure, which may be attributed to the vacancy-ordered domains being smaller than the size of the crystallites and/or the presence of anti-phase boundaries, faulting or other disorder effects. The intermediate stoichiometry between that of γ-Fe 2 O 3 and Fe 3 O 4 is confirmed by refinement of the Fe/O stoichiometry in the scattering data and quantitative analysis of Mössbauer spectra. The structural characterization is complemented by nano/micro-structural analysis using transmission electron microscopy (TEM), elemental mapping using scanning TEM, energy-dispersive X-ray spectroscopy and the measurement of macroscopic magnetic properties using vibrating sample magnetometry. Notably, no evidence is found of a Fe 3 O 4 /γ-Fe 2 O 3 core-shell nanostructure being present, which had previously been suggested for non-stoichiometric spinel iron oxide nanoparticles. Finally, the study is concluded using the magnetic PDF (mPDF) method to model the neutron total-scattering data and determine the local magnetic ordering and magnetic domain sizes in the iron oxide nanoparticles. The mPDF data analysis reveals ferrimagnetic collinear ordering of the spins in the structure and the magnetic domain sizes to be ∼60–70% of the total nanoparticle sizes. The present study is the first in which mPDF analysis has been applied to magnetic nanoparticles, establishing a successful precedent for future studies of magnetic nanoparticles using this technique.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2026

Towards time-resolved MicroED grid preparation using mix-and-inject gas dynamic virtual nozzles

Recent progress in gas dynamic virtual nozzle (GDVN) technologies in combination with high-brilliance synchrotron and X-ray free-electron lasers (XFELs) has allowed the visualization of protein dynamics in crystallo by mixing macromolecular protein crystals with a substrate using tunable mixing times on the order of milliseconds to seconds prior to serial X-ray diffraction data collection. This has become the method of choice for high-resolution structure determination of intermediate states. However, such experiments require large counts of crystals of proper sizes for high-resolution data collection, and premium beam times for screening efforts. Cryogenic microcrystal electron diffraction (MicroED) represents a complementary technique that may be a more accessible avenue for time-resolved nanocrystallography compared with serial X-ray diffraction experiments. MicroED can produce full diffraction datasets from just a few submicrometre-thick crystals, and the approach is more readily accessible, requiring standard cryogenic transmission electron microscopy (TEM) equipment available at many universities and institutes. Cryogenic MicroED, like other forms of cryo-EM, begins with rapidly freezing biological material on electron microscopy grids. In the case of MicroED, micro- to nano-crystals (<500 nm thick) are deposited onto electron microscopy grids and plunge-frozen for subsequent electron diffraction data collection. Here, we have incorporated GDVN technology developed originally for XFEL experiments into the freezing process as a first step towards time-resolved studies. We describe the limited deposition efficiency of the model MicroED protein proteinase K on TEM grids using GDVNs, preceding sample vitrification and successful MicroED data collection. We discuss both the initial results from such experiments and the methodological challenges in developing this approach into a reliable workflow for millisecond-to-second time-resolved structural studies of macromolecules. Our results promise a strategy to deposit crystals on grids using GDVNs and determine high-resolution structures by MicroED, constituting a first step towards development of time-resolved MicroED experiments.

MicroED↗

DOE OSTI2021

Cross Section Measurements of Photonuclear Reaction Pathways Towards Promising Medical Radioisotopes

Project Objectives: The goal of this project was to generate data relevant to radioisotope production while developing innovative technologies that foster and enhance novel production of radioisotopes, and, also, while providing opportunities for cultivating and training future generations of scientists. This work has provided the foundation for methodologies for determination of photonuclear cross sections over multiple energies in a single irradiation. Simultaneously, the feasibility of electron LINAC production of several in-demand radioisotopes such as 47 Sc, 67 Cu, 77 As, and 186 Re has been demonstrated. To accomplish these objectives a collaboration was formed between two complimentary facilities, the Low Energy Accelerator Facility (LEAF) at Argonne National Laboratory and the High Intensity Gamma-ray Source (HIGS) at Triangular Universities Nuclear Laboratory (TUNL). The involvement of the research group from North Carolina Central University gave students at this Historically Black University experience in forefront nuclear-physics research relevant to addressing a high-priority interdisciplinary issue. Project Description: HIGS provides a nearly monoenergetic gamma-ray beam by intra-cavity Compton backscattering of free-electron photons from electrons circulating in a storage ring. This beam can be collimated to produce a very precise energy beam. If the beam is un-collimated a calculated and precise energy spread of the beam occurs radially. The γ-flux can be evenly distributed over the radial distribution of energy and used to perform activation experiments on concentric ring targets. Thus providing multiple energy ranges in a single irradiation. Each concentric ring target can be counted separately in order to determine activation at the given energy and successively be correlated to the activation cross section. Targets were activated to determine production feasibility using electron beams at LEAF. Potential Impact: The Nuclear Science Advisory Committee recently named production of radioisotopes with electron LINACs as one of the most compelling and largest-impact opportunities for the production of high specific activity radioisotopes. Improving the photonuclear cross sectional data base with experimentally verified results will greatly enhance a researcher’s ability to rationalize electron LINAC production routes towards desired radioisotopes. This work will provide the foundation for methodologies for determination of photonuclear cross sections over multiple energies and multiple targets in a single irradiation. The techniques developed in this project will enable future studies to continue verifying theoretically predicted photonuclear cross section with experimental results. These data will also enable adaptation of models and support more precise theoretical calculation of photonuclear cross sections. This research will involve undergraduates, graduate students, and post-docs to give them a valuable research experience leading towards the next generation of scientists in the field of medical isotopes.

07 ISOTOPE AND RADIATION SOURCES↗

NASA NTRS2000

Test Cases for a Rectangular Supercritical Wing Undergoing Pitching Oscillations

Steady and unsteady measured pressures for a Rectangular Supercritical Wing (RSW) undergoing pitching oscillations have been presented. From the several hundred compiled data points, 27 static and 36 pitching oscillation cases have been proposed for computational Test Cases to illustrate the trends with Mach number, reduced frequency, and angle of attack. The wing was designed to be a simple configuration for Computational Fluid Dynamics (CFD) comparisons. The wing had an unswept rectangular planform plus a tip of revolution, a panel aspect ratio of 2.0, a twelve per cent thick supercritical airfoil section, and no twist. The model was tested over a wide range of Mach numbers, from 0.27 to 0.90, corresponding to low subsonic flows up to strong transonic flows. The higher Mach numbers are well beyond the design Mach number such as might be required for flutter verification beyond cruise conditions. The pitching oscillations covered a broad range of reduced frequencies. Some early calculations for this wing are given for lifting pressure as calculated from a linear lifting surface program and from a transonic small perturbation program. The unsteady results were given primarily for a mild transonic condition at M = 0.70. For these cases the agreement with the data was only fair, possibly resulting from the omission of viscous effects. Supercritical airfoil sections are known to be sensitive to viscous effects (for example, one case cited). Calculations using a higher level code with the full potential equations have been presented for one of the same cases, and with the Euler equations. The agreement around the leading edge was improved, but overall the agreement was not completely satisfactory. Typically for low-aspect-ratio rectangular wings, transonic shock waves on the wing tend to sweep forward from root to tip such that there are strong three-dimensional effects. It might also be noted that for most of the test, the model was tested with free transition, but a few points were taken with an added transition strip for comparison. Some unpublished results of a rigid wing of the same airfoil and planform that was tested on the pitch and plunge apparatus mount system (PAPA) showed effects of the lower surface transition Strip on flutter at the lower subsonic Mach numbers. Significant effects of a transition strip were also obtained on a wing with a thicker supercritical section on the PAPA mount system. Both of these flutter tests on the PAPA resulted in very low reduced frequencies that may be a factor in this influence of the transition strip. However, these results indicate that correlation studies for RSW may require some attention to the estimation of transition location to accurately treat viscous effects. In this report several Test Cases are selected to illustrate trends for a variety of different conditions with emphasis on transonic flow effects. An overview of the model and tests is given and the standard formulary for these data is listed. Sample data points are presented in both tabular and graphical form. A complete tabulation and plotting of all the Test Cases is given. Only the static pressures and the real and imaginary parts of the first harmonic of the unsteady pressures are available. All the data for the test are available in electronic file form. The Test Cases are also available as separate electronic files.

Bennett, Robert M.↗

DOE OSTI2022

Machine learning the metastable phase diagram of covalently bonded carbon

Abstract Conventional phase diagram generation involves experimentation to provide an initial estimate of the set of thermodynamically accessible phases and their boundaries, followed by use of phenomenological models to interpolate between the available experimental data points and extrapolate to experimentally inaccessible regions. Such an approach, combined with high throughput first-principles calculations and data-mining techniques, has led to exhaustive thermodynamic databases (e.g. compatible with the CALPHAD method), albeit focused on the reduced set of phases observed at distinct thermodynamic equilibria. In contrast, materials during their synthesis, operation, or processing, may not reach their thermodynamic equilibrium state but, instead, remain trapped in a local (metastable) free energy minimum, which may exhibit desirable properties. Here, we introduce an automated workflow that integrates first-principles physics and atomistic simulations with machine learning (ML), and high-performance computing to allow rapid exploration of the metastable phases to construct “metastable” phase diagrams for materials far-from-equilibrium. Using carbon as a prototypical system, we demonstrate automated metastable phase diagram construction to map hundreds of metastable states ranging from near equilibrium to far-from-equilibrium (400 meV/atom). We incorporate the free energy calculations into a neural-network-based learning of the equations of state that allows for efficient construction of metastable phase diagrams. We use the metastable phase diagram and identify domains of relative stability and synthesizability of metastable materials. High temperature high pressure experiments using a diamond anvil cell on graphite sample coupled with high-resolution transmission electron microscopy (HRTEM) confirm our metastable phase predictions. In particular, we identify the previously ambiguous structure of n -diamond as a cubic-analog of diaphite-like lonsdaelite phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

One- and two-qubit gate infidelities due to motional errors in trapped ions and electrons

In this work, we derive analytic formulas that determine the effect of error mechanisms on one- and two-qubit gates in trapped ions and electrons. First, we analyze and derive expressions for the effect of driving field inhomogeneities on one-qubit gate fidelities. Second, we derive expressions for two-qubit gate errors, including static motional frequency shifts, trap anharmonicities, field inhomogeneities, heating, and motional dephasing. We show that, for small errors, each of our expressions for infidelity converges to its respective numerical simulation; this shows that our formulas are sufficient for determining error budgets for high-fidelity gates, obviating numerical simulations in future projects. All of the derivations are general to any internal qubit state, and any mixed state of the ion crystal's motion that is diagonal in the Fock state basis. Our treatment of static motional frequency shifts, trap anharmonicities, heating, and motional dephasing apply to both laser-based and laser-free gates, while our treatment of field inhomogeneities applies to laser-free systems.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS2019

Quantifying the Influence of Redox Conditions on the Seismic Properties of Olivine

A series of eight olivine specimens were fabricated by hot-pressing at 1200 degrees Celsius and 300 megapascals (MPa). Each hot-pressed specimen was then wrapped in Pt, Ni or NiFe foil to vary oxygen fugacity (fO2), and interrogated via forced torsional oscillation. Mechanical testing was conducted at 10 oscillation periods between 1 and 1000 seconds, at a confining pressure of 200 MPa, during a slow staged-cooling from a maximum temperature of 1200 degrees Celsius to room temperature. After mechanical testing, each specimen was axially sectioned and EBSD (Electron BackScatter Diffraction) was used for the determination of the representative grain size, and grain size distribution of each sample. In addition, each longitudinal section was mapped via FTIR (Fourier Transform InfraRed spectroscopy) to determine the spatial distribution and concentrations of chemically bound and molecular water. Amongst these specimens, chemically bound ‘water’ contents were observed to vary between 0 and 1150 atom ppm (parts per million) H/Si, and molecular water concentrations varied between 0 and 245 atom ppm H/Si. Our forced-oscillation results demonstrate that the measured magnitude of anelastic relaxation within the experimental ‘window’ of oscillation periods is unrelated to the water content. Rather, a relationship was observed between the magnitude of anelastic relaxation and the prevailing redox conditions, which is influenced by the choice of metal sleeving used during the mechanical test. Further, regardless of water content or metal sleeving, each specimen exhibits coupled variations in shear modulus and dissipation within the observational window, indicative of ‘high-temperature background’ behavior, that can be described by a Burgers-type model. During initial fitting of the Burgers models, the unrelaxed shear modulus at a reference temperature of 900 degrees Celsius (G (sub UR)) and the temperature derivative of the unrelaxed shear modulus (dG (sub U)/dT), were treated as adjustable parameters. For all Fe-bearing olivine samples (but not a hydrous and oxidized Fe-free sample) we observe deficits of G (sub UR), and increased values of dG (sub U)/dT, relative to the expected elastic (anharmonic) behavior of Fo90 olivine. This behavior is indicative of anelastic relaxation occurring at shorter periods than observable within the ‘window’ of oscillation periods used in the mechanical test. Moving towards a comprehensive seismologically applicable Burgers model, which includes this newly observed effect of redox conditions on anelastic relaxation, we will present our progress in reconciling truly anharmonic and elastic behavior of Fo (sub 90) olivine with our observed forced-oscillation data.

Cline, Christopher, II↗

DOE OSTI2025

Mapping the gas density with the kinematic Sunyaev-Zel’dovich and patchy screening effects: A self-consistent comparison

The secondary anisotropies of the cosmic microwave background (CMB) provide a wealth of astrophysical and cosmological information. Pairing measurements of the CMB temperature map obtained by DR5 of the Atacama Cosmology Telescope (ACT) with the imaging survey conducted by the Dark Energy Spectroscopic Instrument for the purposes of target selection, DECaLS DR9, we investigate two effects that are sensitive to the gas density 𝜏: kinematic Sunyaev-Zel’dovich (kSZ) and patchy screening or anisotropic screening (resulting from the Thomson scattering of CMB photons away from the line-of-sight by free electrons). In particular, we measure the stacked profiles of the gas density around luminous red galaxies (LRGs) at a mean redshift of 𝑧 ≈ 0.7. We detect the kSZ signal at 7.2⁢𝜎, and we find a signal at ∼ 4.1⁢𝜎 for the patchy screening estimator, which is in excess relative to the kSZ signal. We attribute this excess to contamination from CMB lensing. Here, we demonstrate the effect of lensing using 𝑁-body simulations, and we show that the screening signal is dominated by it. Accounting for lensing, our measurement places a 95% upper bound on the optical depth of the Extended DESI LRG sample of 𝜏 < 2.5 10 −4 for a mean value of the sample of 𝜏 ≈ 1.6 10 −4 . Furthermore, via hydro simulations, we show that the underlying optical depth signal measured by both effects (after removing the CMB lensing contribution) is in perfect agreement when adopting either a compensated aperture photometry (CAP) filter or a high-pass filter. Consistent with previous measurements, we see evidence for excess baryonic feedback around DESI LRGs in the patchy screening measurement. In the future, when both effects can be measured with high signal-to-noise, one can measure the amplitude ratio between them, which is proportional to the root-mean-square velocity of the host halo sample, and even place constraints on velocity-sensitive models such as modified gravity and phantom dark energy.

Astrophysical & cosmological simulations↗

DOE OSTI2020

A Pd III Sulfate Dimer Initiates Rapid Methane Monofunctionalization by H Atom Abstraction

An electrogenerated Pd III 2 species in fuming sulfuric acid is competent for rapid and concurrent methane monohydroxylation to methyl bisulfate (CH 3 OSO 3 H) and methane sulfonation to methanesulfonic acid (CH 3 SO 3 H). In situ NMR at 50 °C is used to track methane transformation exclusively to CH 3 OSO 3 H and CH 3 SO 3 H at high conversions. Integrating a set of kinetic and computational studies, the mechanism of methane monofunctionalization by Pd III 2 is examined. Here, experimental rate laws and common kinetic isotope effects for CH 3 OSO 3 H and CH 3 SO 3 H formation suggest that both transformations proceed via a common rate-limiting C-H activation step. Introduction of O 2 or Pd II,III 2 suppresses CH 3 SO 3 H generation, indicating a radical chain sequence. Although the metal-metal bonded Pd III 2 complex is a net two-electron oxidant, our aggregate kinetic data point to a mechanistic model that features rate-limiting H atom abstraction by the Pd III 2 complex to generate a methyl radical intermediate. The CH 3 • intermediate then recombines with Pd II,III 2 to furnish a CH 3 Pd III 2 intermediate that reductively eliminates CH 3 OSO 3 H. Alternatively, the CH 3 intermediate can enter a chain reaction with SO 3 to generate CH 3 SO 3 H. DFT computations support the radical-based C-H activation by Pd III 2 and delineate H atom abstraction pathways with computed reaction barriers and kinetic isotope effects (KIEs) that are consistent with experimental data. These mechanistic investigations challenge the paradigm of electrophilic C-H activation and highlight H atom abstraction as a potent pathway for selective methane C-H oxidative functionalization at high reaction rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗