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At least 577 records · Page 32

Ultrafast X-ray Spectroscopy of Intersystem Crossing in Hexafluoroacetylacetone: Chromophore Photophysics and Spectral Changes in the Face of Electron-Withdrawing Groups

Intersystem crossings between singlet and triplet states represent a crucial relaxation pathway in photochemical processes. Herein, we probe the intersystem crossing in hexafluoro-acetylacetone with ultrafast X-ray transient absorption spectroscopy at the carbon K-edge. In this study, we observe the excited state dynamics following excitation with 266 nm UV light to the 1 ππ* (S 2 ) state with element and site-specificity using a broadband soft X-ray pulse produced by high harmonic generation. These results are compared to X-ray spectra computed from orbital optimized density functional theory methods. It is found that the electron-withdrawing fluorine atoms decongest the X-ray absorption spectrum by enhancing separation between features originating from different carbon atoms. This facilitates the elucidation of structural and electronic dynamics at the chromophore. The evolution of the core-to-valence resonances at the carbon K-edge reveals an ultrafast population transfer between the 1 nπ* (S 1 ) and 3 ππ* (T 1 ) states on a 1.6 ± 0.4 ps time scale, which is similar to the 1.5 ps time scale earlier observed for acetylacetone [ J. Am. Chem. Soc. 2017, 139, 16576—16583, DOI: 10.1021/jacs.7b07532]. It therefore appears that terminal fluorination has little influence on the intersystem crossing rate of the acetylacetone chromophore. In addition, the significant role of hydrogen-bond opened and twisted rotational isomers is elucidated in the excited state dynamics by comparison of the experimental transient X-ray spectra with theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local primordial non-Gaussian bias from time evolution

Primordial non-Gaussianity (PNG) is a signature of fundamental physics in the early Universe that is probed by cosmological observations. Here, it is well known that the local type of PNG generates a strong signal in the two-point function of large-scale structure tracers, such as galaxies. This signal, often termed “scale-dependent bias” is a generic feature of modulation of gravitational structure formation by a large-scale mode. It is less well appreciated that the coefficient controlling this signal, b ϕ , is closely connected to the time evolution of the tracer number density. This correspondence between time evolution and local PNG can be simply explained for a universal tracer whose mass function only depends on peak height and, more generally, for nonuniversal tracers in the separate universe picture, which we validate in simulations. We also describe how to recover the bias of tracers subject to a survey selection function and perform a simple demonstration on simulated galaxies. Since the local PNG amplitude in n-point statistics ($f$ NL ) is largely degenerate with the coefficient b ϕ , this proof of concept study demonstrates that Galaxy survey data can allow for more optimal and robust extraction of local PNG information from upcoming surveys.

Sullivan, James M. [University of California, Berk↗

Time scales and variability of area-averaged tropical oceanic rainfall

A statistical analysis of time series of area-averaged rainfall over the oceans has been conducted around the diurnal time scale. The results of this analysis can be applied directly to the problem of establishing the magnitude of expected errors to be incurred in the estimation of monthly area-averaged rain rate from low orbiting satellites. Such statistics as the mean, standard deviation, integral time scale of background red noise, and spectral analyses were performed on time series of the GOES precipitation index taken at 3-hour intervals during the period spanning December 19, 1987 to March 31, 1988 over the central and eastern tropical Pacific. The analyses have been conducted on 2.5 x 2.5 deg and 5 x 5 deg grid boxes, separately. The study shows that rainfall measurements by a sun-synchronous satellite visiting a spot twice per day will include a bias due to the existence of the semidiurnal cycle in the SPCZ ranging from 5 to 10 percentage points. The bias in the ITCZ may be of the order of 5 percentage points.

Shin, Kyung-Sup↗

Flowfield measurements in a separated and reattached flat plate turbulent boundary layer

The separation and reattachment of a large-scale, two-dimensional turbulent boundary layer at low subsonic speed on a flat plate has been studied experimentally. The separation bubble was 55 cm long and had a maximum bubble thickness, measured to the height of the mean dividing streamline, of 17 cm, which was twice the thickness of the inlet boundary layer. A combination of laser velocimetry, hot-wire anemometry, pneumatic probing techniques, and flow visualization were used as diagnostics. Principal findings were that an outer inviscid rotational flow was defined which essentially convected over the blockage associated with the inner, viscously dominated bubble recirculation region. A strong backflow region in which the flow moved upstream 100 percent of the time was measured near the test surface over the central 35 percent of the bubble. A laminar backflow boundary layer having pseudo-turbulent characteristics including a log-linear velocity profile was generated under the highly turbulent backflow. Velocity profile shapes in the reversed flow region matched a previously developed universal backflow profile at the upstream edge of the separation region but not in the steady backflow region downstream. A smoke flow visualization movie and hot-film measurements revealed low frequency nonperiodic flapping at reattachment. However, forward flow fraction data at reattachment and mean velocity profiles in the redeveloping boundary layer downstream of reattachment correlated with backward-facing step data when the axial dimension was scaled by the distance from the maximum bubble thickness to reattachment.

Patrick, William P.↗

Electrically Powered High-Salinity Brine Separation Using Dimethyl Ether

Dewatering highly saline aqueous streams, from mining and geothermal leachates to industrial wastewater, is essential for effective resource recovery and safe disposal. Membraneless water extraction (MWE) uses a low-polarity solvent to separate water from concentrated aqueous solutions. In this study, we design a new MWE that uses dimethyl ether (DME) to selectively extract water from high-salinity brines, leveraging the volatility of DME to achieve rapid solvent recovery. By separating water and dissolved salts at a liquid–liquid interface, MWE minimizes the deleterious effects of scaling on vulnerable membrane and heat exchanger surfaces, reducing the need for extensive pretreatment and expensive materials. We begin by developing a computational framework for a multistage counterflow liquid–liquid contactor, which extracts water into DME, coupled with a multistage solvent regenerator that uses vapor compression to efficiently separate the desalinated water from the DME extractant. Excess Gibbs free energy and equation of state frameworks are used to model fluid phase equilibria in water–DME–sodium chloride (NaCl) mixtures, with interaction parameters estimated from experimental data. Incorporating equilibrium calculations into a system-scale computational model, we examine the performance of MWE using DME for the first time. Our analysis demonstrates that MWE can concentrate seawater desalination brine (>1.0 mol NaCl kg –1 ) to zero-liquid discharge salinities, with an energy consumption of under 50 kW h per m 3 of water extracted with a solvent recovery ratio greater than 99.9%. We highlight the importance of staging the vapor compression process to simultaneously minimize energy consumption while enabling brine concentration and product water solvent contamination. Finally, the thermodynamic framework developed here allows for the robust evaluation of new MWE solvents and systems for critical brine concentration and fractional precipitation applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale covariance magnetometry with diamond quantum sensors

Nitrogen vacancy (NV) centers in diamond are atom-scale defects that can be used to sense magnetic fields with high sensitivity and spatial resolution. Typically, the magnetic field is measured by averaging sequential measurements of single NV centers, or by spatial averaging over ensembles of many NV centers, which provides mean values that contain no nonlocal information about the relationship between two points separated in space or time. In this work, we propose and implement a sensing modality whereby two or more NV centers are measured simultaneously, and we extract temporal and spatial correlations in their signals that would otherwise be inaccessible. We demonstrate measurements of correlated applied noise using spin-to-charge readout of two NV centers and implement a spectral reconstruction protocol for disentangling local and nonlocal noise sources.

47 OTHER INSTRUMENTATION↗

On the structure of contact binaries. I - The contact discontinuity

The problem of the interior structure of contact binaries is reviewed, and a simple resolution of the difficulties which plague the theory is suggested. It is proposed that contact binaries contain a contact discontinuity between the lower surface of the common envelope and the Roche lobe of the cooler star. This discontinuity is maintained against thermal diffusion by fluid flow, and the transition layer is thin to the extent that the dynamical time scale is short in comparison with the thermal time scale. The idealization that the transition layer has infinitesimal thickness allows a simple formulation of the structure equations which are closed by appropriate jump conditions across the discontinuity. The further imposition of the standard boundary conditions suffices to define a unique model for the system once the chemical composition, the masses of the two stars, and the orbital separation are specified.

Shu, F. H.↗

Solar pressure and molecular decay in cometary atmospheres

The effects of solar pressure and molecular decay on number density in cometary atmospheres are rigorously separated and scale lengths for each are determined from an analysis of observed brightness profiles in the solar and antisolar directions. It is found that the pressure scale length of CN is approximately 160,000 km and that of C2 is approximately 110,000 km. The scale length for molecular decay, heretofore incorrectly inferred from the observational data, is approximately 3 times as long as the pressure scale lengths. It is difficult to determine adequately from observations that extend no more than about 100,000 km from the comet nucleus. The scale length for molecular decay by photodissociation or whatever cause is found to be about 350,000 km for C2 and 500,000 km for CN.

Beard, D. B.↗

Models for multiple heating mechanisms

Current meteoritic and astrophysical evidence (especially FU Orionis events) suggests that large-scale gas-dynamics shocks penetrating to the nebular midplane represent a promising class of multiple heating mechanisms for the formation of chondrules. Initial numerical models have shown that shock heating of chondrule precursor grains in optically thick clouds of grains is especially efficient. Shocks generated by infalling molecular cloud clumps and shocks separating different mass elements in a time dependently and axially asymmetrically evolving disk are possibilities deserving further attention. Meteoritic constraints, astrophysical considerations and multiple heating mechanisms are addressed.

Hood, L. L.↗

Progress Towards Integrating the Finite-Volume Cubed-Sphere (FV3) Dynamical Core Tangent Linear and Adjoint Models into JEDI

The Joint Effort for Data assimilation Integration (JEDI) -- led by the Joint Center for Satellite Data Assimilation (JCSDA) -- is an inter-organizational endeavor to develop a common framework for performing data assimilation. This extensive framework will ultimately provide solvers, observation operators, interpolation and model interfaces using object oriented modeling. Two partners involved in JEDI use or plan to use the Finite Volume Cubed-Sphere (FV3) dynamical core to produce weather forecasts; these are NASA's Global Modeling and Assimilation Office and NOAA's National Center for Environment Prediction. In this work we present an update on ongoing efforts to integrate the FV3 tangent linear and adjoint models into the prototype JEDI framework. We setup and run a simple cycled data assimilation experiment using 4DVAR on the cubed sphere grid and with the FV3 tangent linear and adjoint models. Development of the observation operators for JEDI is separately underway. Instead of using real observations a simplified set of simulated observations will be used. We discuss the steps required to bring the FV3 linearized model into the object oriented framework and consider what would be the computational requirements of running this configuration for an operational system. FV3 uses a small time-step to ensure that small scales are well resolved, however this presents design challenges when running 4DVAR with the adjoint. An approach to storing the FV3 model trajectory has been developed that maintains the flexibility of using automatic differentiation. We discuss how this approach is incorporated into the framework. Other important uses of adjoint models include computing observation impacts and singular vectors, we consider how these tools can be included in JEDI.

Holdaway, Daniel↗

Constraining dark matter substructure with Gaia wide binaries

ABSTRACT We use a catalogue of stellar binaries with wide separations (up to 1 pc) identified by the Gaia satellite to constrain the presence of extended substructure within the Milky Way galaxy. Heating of the binaries through repeated encounters with substructure results in a characteristic distribution of binary separations, allowing constraints to be placed independent of the formation mechanism of wide binaries. Across a wide range of subhalo density profiles, we show that subhaloes with masses $\gtrsim 65\, \mathrm{ M}_\odot$ and characteristic length scales similar to the separation of these wide binaries cannot make up 100 per cent of the Galaxy’s dark matter. Constraints weaken for subhaloes with larger length scales and are dependent on their density profiles. For such large subhaloes, higher central densities lead to stronger constraints. Subhaloes with density profiles similar to those expected from cold dark matter must be at least ∼5000 times denser than predicted by simulation to be constrained by the wide binary catalogue.

Astronomy & Astrophysics↗

FORCE Update 2024

The Framework for Optimization of Resources and Economics (FORCE) tool suite is the U.S. Department of Energy’s Nuclear Integrated Energy Systems (IES) Program flagship tool suite for technoeconomic IES analysis of IES. This tool suite is useful for analysis designed to evaluate and improve the technoeconomics of energy production systems, particularly for systems including nuclear technology. In this report, we document the development activity for the FORCE tool suite to extend its capabilities as performed during fiscal year 2024. In addition to reliability and accessibility, capability is one of the three standards guiding the development of the FORCE tool suite and the software codes that are its constituent parts. Extending the capabilities of the FORCE tool suite allows analysis both within the IES program as well as industry, university, and laboratory partners to perform analysis with more accuracy, insight, and impactful narrative. Four areas of capability development were the focus of activity this year: economic parameter uncertainty quantification, multiresolution analysis, components-to-optimization workflow automation, and statespace construction workflows for real-time optimal control. In economic parameter uncertainty quantification, the ability of HERON to capture risk due to scenarios (weather and energy demand uncertainty) was expanded to also include uncertainties in financial parameters such as capital cost or operation and maintenance costs. By including these sources of uncertainty, which are sometimes very large compared with scenario uncertainty, HERON is better able to capture the risk posed by investment in various IES technology. Because of this, analysts can also consider the reduction in risks that can be realized by choice of some technologies. In multiresolution analysis, development activity extended on work completed previously. In fiscal year 2023, methods for decomposing time series signals, such as demand, solar and wind availability, and price profiles, were analyzed and down-selected to those most effective at splitting signals into different resolutions. These resolutions allow considering the influence of different energy demand and supply behaviors across different time scales. For example, energy demand might be divided into seasonal, weekly, and hourly profiles. In fiscal year 2024, this preliminary work was extended and implemented within the Risk Analysis Virtual Environment (RAVEN) risk and uncertainty analysis platform, which is used throughout the FORCE framework. This development of the “multi-resolution time series analysis” (MR-TSA) module in RAVEN allows training synthetic history generators on complex time series. These synthetic history generators can then be used in HERON for generating scenarios that represent possible market and weather scenarios that can be analyzed on different time scales. We envision completing this work in the future, implementing multiresolution dispatch optimization strategies that can make the most beneficial use of these stratified time histories. In components-to-optimization workflow development, workflows for translating user inputs of components into algorithms for algebraic optimization were selected and implemented. Similar algorithms within the Holistic Energy Resource Optimization Network (HERON) were separated from the main code base of HERON and gathered with the components-to-optimization workflows in the new Dispatch Optimization Variable Engine (DOVE) software library. This modularization allows FORCE users to analyze dispatch optimization and energy system duty cycles independently of HERON, which previously was a burdensome task. Additionally, these dispatch optimization algorithms, set up in an independent library, can now be used across all software applications within FORCE, especially including the real-time optimal control software Optimization of Real-time Capacity Allocation (ORCA). Allowing FORCE software to share dispatch optimization algorithms within a single library allows for improved software maintenance and reliability. In statespace characterization workflow development, alternative workflows for optimizing dispatch with additional technical accuracy was the focus, particularly to improve the real-time optimization decision making in ORCA. Using algorithms and workflows initially developed for the Feasible Actuator Range Modifier (FARM), workflows for determining the statespace representation of IES were identified and demonstrated. The resulting dispatch optimization required a more robust optimization algorithm than that originally used in HERON (and moved to DOVE), which required adding an alternate workflow to DOVE that can more accurately match the behavior of physical systems using a partial differential equation representation. In conclusion, capability developments in the FORCE tool suite in fiscal year 2024 have improved the ability of the FORCE tool suite to perform

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Interannual and Decadal Variability of Ocean Surface Latent Heat Flux as Seen from Passive Microwave Satellite Algorithms

Ocean surface turbulent fluxes are critical links in the climate system since they mediate energy exchange between the two fluid systems (ocean and atmosphere) whose combined heat transport determines the basic character of Earth's climate. Deriving physically-based latent and sensible heat fluxes from satellite is dependent on inferences of near surface moisture and temperature from coarser layer retrievals or satellite radiances. Uncertainties in these "retrievals" propagate through bulk aerodynamic algorithms, interacting as well with error properties of surface wind speed, also provided by satellite. By systematically evaluating an array of passive microwave satellite algorithms, the SEAFLUX project is providing improved understanding of these errors and finding pathways for reducing or eliminating them. In this study we focus on evaluating the interannual variability of several passive microwave-based estimates of latent heat flux starting from monthly mean gridded data. The algorithms considered range from those based essentially on SSM/I (e.g. HOAPS) to newer approaches that consider additional moisture information from SSM/T-2 or AMSU-B and lower tropospheric temperature data from AMSU-A. On interannual scales, variability arising from ENSO events and time-lagged responses of ocean turbulent and radiative fluxes in other ocean basins (as well as the extratropical Pacific) is widely recognized, but still not well quantified. Locally, these flux anomalies are of order 10-20 W/sq m and present a relevant "target" with which to verify algorithm performance in a climate context. On decadal time scales there is some evidence from reanalyses and remotely-sensed fluxes alike that tropical ocean-averaged latent heat fluxes have increased 5-10 W/sq m since the early 1990s. However, significant uncertainty surrounds this estimate. Our work addresses the origin of these uncertainties and provides statistics on time series of tropical ocean averages, regional space / time correlation analysis, and separation of contributions by variations in wind and near surface humidity deficit. Comparison to variations in reanalysis data sets is also provided for reference.

Robertson, Franklin R.↗

Rapid charging made practical in graphite-based lithium batteries: surface-acoustic wave turbulent electrolyte mixing to overcome diffusion limited charging rates [Final Report]

One of the key limits in rapidly recharging a lithium-ion battery is the depletion of lithium ions within the electrolyte adjacent the anode during charging and long diffusion time to overcome this depletion. It also causes dendrite formation, inefficient use of the lithium, and battery degradation over many charge-discharge cycles. Because the liquid electrolyte remains quiescent and unmixed, this depletion layer’s depth rapidly grows to match the anode-cathode separation distance at even modest charge rates. The solution proposed by PI Prof. James Friend and Co-PI Prof. Ping Liu, both from the University of California, San Diego, is to mix the electrolyte and minimize the Li+ ion concentration gradient during charging. Even in the presence of the separator, the charging rate could then be significantly increased. They propose to accomplish this using surface acoustic wave (SAW)-driven acoustic streaming, a technique employing 10-mW fingernail-sized solid-state devices from the telecommunications industry to drive turbulent mixing to submicron length scales in a manner completely compatible with the typical 20700 and 18650 cells used in electric vehicles. 0.1. Turbulent acoustic streaming mixes the electrolyte during charging—even with separator Our proposed 100-MHz SAW device used to recirculate the electrolyte is compatible with lithium- ion battery electrochemistry, as it is made in our lab of single-crystal lithium niobate. Their solution is straightforward to drive from a DC power source alongside the signal provided during battery charging. The device is only needed during charging and does not consume power dur- ing battery discharge. Uniquely, SAW generates extreme accelerations of over 1 billion meters per second squared in the fluid, driving turbulent mixing from centimeter to submicron length scales, even through the porous separator materials that tend to be used in batteries, all while avoiding interfering with the anode’s solid electrolyte interphase layer that forms during use. By employing novel fluid mechanics, the investigators are proposing a new direction for battery research away from direct use of materials science and electrochemistry. The chemistry agnostic solution may be employed in any battery chemistry that makes use of liquid electrolytes, providing a broader transformative benefit to the battery research community. They are to produce a series of prismatic and 20700-cell sized 2 Ah batteries capable of being charged and discharged at least 500 times without more than 20% loss in battery capacity, and to provide analysis tools useful to the battery research and development community for adopting this approach for other battery chemistries and configurations.

25 ENERGY STORAGE↗

Mass-conserving implicit–explicit methods for coupled compressible Navier–Stokes equations

Earth system models are composed of coupled components that separately model systems such as the global atmosphere, ocean, and land surface. While these components are well developed, coupling them in a single system can be a significant challenge. Computational efficiency, accuracy, and stability are principal concerns. In this study we focus on these issues. In particular, implicit–explicit (IMEX) tight and loose coupling strategies are explored for handling different time scales. For a simplified model for the air–sea interaction problem, we consider coupled compressible Navier–Stokes equations with an interface condition. Under the rigid-lid assumption, horizontal momentum and heat flux are exchanged through the interface. Several numerical experiments are presented to demonstrate the stability of the coupling schemes. Here, we show both numerically and theoretically that our IMEX coupling methods are mass conservative for a coupled compressible Navier–Stokes system with the rigid-lid condition

42 ENGINEERING↗

Unified and optimal frame choice for generalized parton distributions

Reconstructing the internal three-dimensional quark and gluon structures of hadrons through generalized parton distributions (GPDs) from hard exclusive scattering processes is one of the most challenging tasks in nuclear and particle physics. In this paper, we introduce a new optimized reference frame that, for the first time, enables a unified view of all the reactions sensitive to GPDs and facilitates the interpretation of a variety of phase-space patterns that were previously hardly accessible and interpretable. Similarly to how the heliocentric description advanced our understanding of the solar system and gravitation, our new frame centers around a quasireal state, allows for a consistent separation of physical scales, and reveals a novel quantum interference mechanism. Published by the American Physical Society 2025

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Unsteady environments and responses of the shuttle combined loads orbiter test

Both separate and combined wind tunnel and vibration shaker tests were conducted on two structural panels representative of the Shuttle orbiter in the NASA LaRC 8-foot transonic pressure tunnel (TPT) to determine the effects of combined loads on the thermal protection system (TPS). The primary objective of this test was to provide a combined full-scale load environment and realistic time history of the dynamic pressures, Mach numbers (through transonic), and dynamic structural responses of these panels. The panels were selected from orbiter locations where interactive load sources such as aerodynamic shock waves, turbulent boundary layers, strut-induced vorticity, and substrate deformation combined to provide high bonding loads between the TPS and the orbiter structure. The test panels for this program were highly instrumented with static and dynamic pressure gages, accelerometers, deflectometers, strain gages, Schileren and high-speed photography, and special instrumentation necessary to determine TPS/structure interface loads and tile motions. Two test specimens of each orbiter panel were utilized. Both were high-fidelity representations of the selected orbiter location. The first panel (calibration panel) for each test was utilized to calibrate the tunnel and shaker system as well as provide a data-gathering source for applied static and dynamic loads. The second panel (test panel) for each test was subjected to flight time exposures only so that TPS characteristics as a function of flight mission exposure could be determined. These tests were the last in a series that was suce6ssfully completed and necessary to certify the TPS prior to the first launching of the Shuttle.

P. H. Schuetz↗

A Method for Calculating Strain Energy Release Rates in Preliminary Design of Composite Skin/Stringer Debonding Under Multi-Axial Loading

Three simple procedures were developed to determine strain energy release rates, G, in composite skin/stringer specimens for various combinations of unaxial and biaxial (in-plane/out-of-plane) loading conditions. These procedures may be used for parametric design studies in such a way that only a few finite element computations will be necessary for a study of many load combinations. The results were compared with mixed mode strain energy release rates calculated directly from nonlinear two-dimensional plane-strain finite element analyses using the virtual crack closure technique. The first procedure involved solving three unknown parameters needed to determine the energy release rates. Good agreement was obtained when the external loads were used in the expression derived. This superposition technique was only applicable if the structure exhibits a linear load/deflection behavior. Consequently, a second technique was derived which was applicable in the case of nonlinear load/deformation behavior. The technique involved calculating six unknown parameters from a set of six simultaneous linear equations with data from six nonlinear analyses to determine the energy release rates. This procedure was not time efficient, and hence, less appealing. A third procedure was developed to calculate mixed mode energy release rates as a function of delamination lengths. This procedure required only one nonlinear finite element analysis of the specimen with a single delamination length to obtain a reference solution for the energy release rates and the scale factors. The delamination was extended in three separate linear models of the local area in the vicinity of the delamination subjected to unit loads to obtain the distribution of G with delamination lengths. This set of sub-problems was Although additional modeling effort is required to create the sub- models, this local technique is efficient for parametric studies.

Krueger, Ronald↗