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At least 577 records · Page 32

Data-Driven Performance Optimization of Gamma Spectrometers With Many Channels

In gamma spectrometers with variable spectroscopic performance across many channels (e.g., many pixels or voxels), a tradeoff exists between including data from successively worse-performing readout channels and increasing efficiency. Brute-force calculation of the optimal set of included channels is exponentially infeasible as the number of channels grows, and approximate methods are required. In this work, we present a data-driven framework for attempting to find near-optimal sets of included detector channels. The framework leverages non-negative matrix factorization (NMF) to learn the behavior of gamma spectra across the detector and clusters similarly-performing detector channels together. Performance comparisons are then made between spectra with channel clusters removed, which is more feasible than brute force. The framework is general and can be applied to arbitrary, user-defined performance metrics depending on the application. We apply this framework to optimizing gamma spectra measured by H3D M400 CdZnTe (CZT) spectrometers, which exhibit variable performance across their crystal volumes. In particular, we show several examples optimizing various performance metrics for uranium and plutonium gamma spectra in non-destructive assay (NDA) for nuclear safeguards, and explore trends in performance versus parameters such as clustering algorithm type. We also compare the NMF + clustering pipeline to several non-machine-learning (ML) algorithms, including several greedy algorithms. Although, we find that the NMF + clustering pipeline tends to find the best-performing set of detector voxels, significantly improving over the unoptimized spectra, but that a greedy accumulation of spectra segmented by detector depth can, in some cases, give similar performance improvements in much less computation time.

Energy resolution↗

Combining Machine Learning and Comparative Effectiveness Methodology to Study Primary Care Pharmacotherapy Pathways for Veterans With Depression

Our objective is to demonstrate an innovative method combining machine learning with comparative effectiveness research techniques and to investigate a hitherto unstudied question about the effectiveness of common prescribing patterns. For Operation Enduring Freedom/Operation Iraqi Freedom veterans with major depressive disorder, we generate pharmacotherapy pathways (of antidepressants) using process mining and machine learning. We select the medication episodes that were started at subtherapeutic doses by the first assigned primary care physician and observe the paths that those medication episodes follow. Using 2-stage least squares, we test the effectiveness of starting at a low dose and staying low for longer versus ramping up fast while balancing observable and unobservable characteristics of patients and providers through instrumental variables. We leverage predetermined provider practice patterns as instruments. We collected outpatient pharmacy data for selective serotonin reuptake inhibitors and selective norepinephrine reuptake inhibitors, patient and provider characteristics (as control variables), and the instruments for our cohort. All data were extracted for the period between 2006 and 2020. There is a statistically significant positive effect (0.68, 95% CI 0.11–1.25) of “ramping up fast” on engagement in care. When we examine the effect of “ramping up slow”, we see an insignificant negative impact on engagement in care (−0.82, 95% CI −1.89 to 0.25). As expected, the probability of drop-out also seems to have a negative effect on engagement in care (−0.39, 95% CI −0.94 to 0.17). We further validate these results by testing with medication possession ratios calculated periodically as an alternative engagement in care metric. Our findings contradict the “Start low, go slow” adage, indicating that ramping up the dose of an antidepressant faster has a significantly positive effect on engagement in care for our population.

60 APPLIED LIFE SCIENCES↗

A Four‐Coordinate Pr 4+ Imidophosphorane Complex

Abstract The imidophosphorane ligand, [NP t Bu 3 ] − ( t Bu= tert ‐butyl), enables isolation of a pseudo‐tetrahedral, tetravalent praseodymium complex, [Pr 4+ (NP t Bu 3 ) 4 ] ( 1‐Pr ), which is characterized by a suite of physical characterization methods including single‐crystal X‐ray diffraction, electron paramagnetic resonance, and L 3 ‐edge X‐ray near‐edge spectroscopies. Variable‐temperature direct‐current magnetic susceptibility data, supported by multiconfigurational quantum chemical calculations, demonstrate that the electronic structure diverges from the isoelectronic Ce 3+ analogue, driven by increased crystal field. The four‐coordinate environment around Pr 4+ in 1‐Pr , which is unparalleled in reported extended solid systems, provides a unique opportunity to study the interplay between crystal field splitting and spin‐orbit coupling in a molecular tetravalent lanthanide within a pseudo‐tetrahedral coordination geometry.

Boggiano, Andrew C.↗

A Four‐Coordinate Pr 4+ Imidophosphorane Complex

Abstract The imidophosphorane ligand, [NP t Bu 3 ] − ( t Bu= tert ‐butyl), enables isolation of a pseudo‐tetrahedral, tetravalent praseodymium complex, [Pr 4+ (NP t Bu 3 ) 4 ] ( 1‐Pr ), which is characterized by a suite of physical characterization methods including single‐crystal X‐ray diffraction, electron paramagnetic resonance, and L 3 ‐edge X‐ray near‐edge spectroscopies. Variable‐temperature direct‐current magnetic susceptibility data, supported by multiconfigurational quantum chemical calculations, demonstrate that the electronic structure diverges from the isoelectronic Ce 3+ analogue, driven by increased crystal field. The four‐coordinate environment around Pr 4+ in 1‐Pr , which is unparalleled in reported extended solid systems, provides a unique opportunity to study the interplay between crystal field splitting and spin‐orbit coupling in a molecular tetravalent lanthanide within a pseudo‐tetrahedral coordination geometry.

Boggiano, Andrew C.↗

Compositional effects on the chemical durabilities of aluminophosphate glasses: A review

Phosphate glasses have a range of applications including as hosts for immobilizing radioactive wastes. Studies have shown that addition of iron and/or aluminum oxides can drastically improve the chemical durability of phosphate glasses where the accurate measurement of chemical durability is one of the most important factors for determining the long-term viability of a given waste form. However, due to inconsistencies with the experimental methods used to generate chemical durability data, comparing and interpreting such data is a tedious task. These variables include the temperature of the test, the specimen form (e.g., coupon, particles), the pressure of the test (e.g., atmospheric pressure, elevated pressure in an autoclave), the exposure time, the exposure medium, and how the loss is documented (e.g., total mass lost, normalized elemental release). This review paper summarizes a large collection of chemical durability tests on aluminophosphate glasses in various studies. In addition, the effects of different oxides on the properties of phosphate glasses are summarized.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Magnetism Studies of Bis(acyl)phosphide-Supported Eu 3+ and Eu 2+ Complexes

A series of bis(acyl)phosphide-supported Eu complexes were synthesized (bis(acyl)phosphide = BAP). Here, in this study, BAP ligands proved to be excellent ligands for the synthesis of both Eu 3+ and Eu 2+ molecular complexes. Sodium bis(mesitoyl)phosphide (Na( mes BAP)) and sodium bis(2,4,6-triisopropylbenzoyl)phosphide (Na( tripp BAP)) were employed as ligand precursors for the synthesis of the Eu 3+ complexes Eu(bis(mesitoyl)phosphide) 3 (thf) 2 (Eu( mes BAP) 3 (thf) 2 ) and Eu(bis(2,4,6-triisopropylbenzoyl)phosphide) 3 (Eu( tripp BAP) 3 ), as well as the Eu 2+ complex, Eu(bis(2,4,6-triisopropylbenzoyl)phosphide) 2 (dme) 2 (Eu( tripp BAP) 2 (dme) 2 ) (thf = tetrahydrofuran, dme = 1,2-dimethoxyethane). All complexes were characterized using a combination of UV–vis–NIR–IR and NMR spectroscopies, and single-crystal X-ray diffraction (SC-XRD). The magnetic properties of these three monomeric Eu complexes were investigated by variable-temperature magnetic susceptibility. The magnetic data are typical for these ions, with Eu( tripp BAP) 2 (dme) 2 displaying Curie-type behavior. Both Eu( tripp BAP) 3 and Eu( mes BAP) 3 (thf) 2 possess similar 7 F 0 - 7 F 1 spin–orbit energy gaps and a similar zero-field splitting of the 7 F 1 state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Leveraging Intramolecular π-Stacking to Access an Exceptionally Long-Lived 3 MC Excited State in an Fe(II) Carbene Complex

The ability to manipulate excited-state decay cascades using molecular structure is essential to the application of abundant-metal photosensitizers and chromophores. Ligand design has yielded some spectacular results elongating charge-transfer excited state lifetimes of Fe(II) coordination complexes, but triplet metal-centered ( 3 MC) excited states - recently demonstrated to be critical to the photoactivity of isoelectronic Co(III) polypyridyls - have to date remained elusive, with temporally isolable examples limited to the picosecond regime. Here, with this report, we show how strong-field donors and intramolecular π-stacking can conspire to stabilize a long-lived 3 MC excited state for a remarkable 4.1 ± 0.3 ns in fluid solution at ambient temperature. Analysis of variable-temperature time-resolved absorption data using theoretical models ranging from Arrhenius to semiclassical Marcus theory, combined with computational modeling and X-ray crystallography, reveal a Jahn−Teller stabilized excited state with a high activation barrier for ground-state recovery. The net result is a chromophore with a 3 MC excited-state lifetime that is orders of magnitude longer than anything yet observed for an Fe(II) complex.

carbene compounds↗

Simultaneous Observations of Surface Layer Profiles of Humidity, Temperature, and Wind Using Scanning Lidar Instruments

We demonstrate the combination of three Doppler lidars (DLs), a water vapor differential absorption lidar and a temperature rotational Raman lidar for the investigation of the interactions between the land-surface and the atmospheric boundary layer. This combination of scanning lidars was operated for the first time during the Land-Atmosphere Feedback Experiment at the Atmospheric Radiation Measurement program's Southern Great Plain site, Oklahoma, USA, in August 2017, and provided simultaneous surface layer profiles of horizontal wind, humidity and temperature. The horizontal wind profiles were determined using the dual-Doppler method with two DLs. The scans were performed above four towers providing atmospheric variables and fluxes. These combined lidar data allowed for the estimation of the friction velocity as well as the surface latent and sensible heat fluxes. For this purpose, profiles calculated with Monin-Obukhov similarity theory were fitted with the Levenberg-Marquardt nonlinear least squares curve-fitting method to the measured surface-layer lidar profiles. We present case studies of three 50-min periods to illustrate the new method. The measurements resulted in friction velocities of 0.31, 0.29, and 0.38 ms –1 , sensible surface heat fluxes of 312.1, 234.1, and 183.3 Wm –2 and latent surface heat fluxes of 251.8, 227.3, and 274.4 Wm –2 . These values were compared with the in-situ measurements of the towers. Considering the sampling differences and the error analyses, the results agree within 25.1%, 42.5%, and 28.8%, respectively, demonstrating that this synergy of scanning active remote sensing systems can be used to derive surface fluxes with reasonable accuracy.

54 ENVIRONMENTAL SCIENCES↗

Representations of Precipitation Diurnal Cycle in the Amazon as Simulated by Observationally Constrained Cloud‐System Resolving and Global Climate Models

Abstract The ability of an observationally‐constrained cloud‐system resolving model (Weather Research and Forecasting; WRF, 4‐km grid spacing) and a global climate model (Energy Exascale Earth System Model; E3SM, 1‐degree grid spacing) to represent the precipitation diurnal cycle over the Amazon basin during the 2014 wet season is assessed. The WRF model coupled with a 3‐D variational data assimilation scheme reproduces the spatial variability of the precipitation diurnal cycle over the basin and the lifecycle of westward propagating MCSs initiated by the coastal sea‐breeze front. In contrast, a single morning peak in rainfall is produced by E3SM for simulations despite the nudging of large‐scale winds toward global reanalysis, indicating precipitation in E3SM is largely controlled by local convection associated with diurnal heating. The role of propagating MCS on the environment are discussed by using a multivariate perturbation analysis. We also find that the advection of moisture perturbations from ocean to inland regions have a higher correlation with the occurrence of MCSs in the Amazon than the intensity of colder air intrusion associated with sea breezes along the coast. Moreover, the presence of large cold pools over the central Amazon basin are responsible for the maintenance of propagating deep convection.

54 ENVIRONMENTAL SCIENCES↗

Empirical Dynamic Modeling Reveals Complexity of Methane Fluxes in a Temperate Salt Marsh

Abstract Methane dynamics within salt marshes are complex because vegetation types, temperature, oscillating water levels, and changes in salinity and redox conditions influence CH 4 production, consumption, oxidation, and emissions. These non‐linear and complex interactions among variables affect the traditionally expected functional relationships and present challenges for interpreting and developing process‐based models. We employed empirical dynamic modeling (EDM) and convergent cross mapping (CCM) as a novel approach for characterizing seasonal/multiday and diurnal CH 4 dynamics by inferring causal variables, lags, and interconnections among multiple biophysical variables within a temperate salt marsh using 5 years of eddy covariance data. EDM/CCM is a nonparametric approach capable of quantifying the coupling between variables while determining time scales where variable interactions are the most relevant. We found that gross primary productivity, tidal creek dissolved oxygen, and temperature were important for seasonal/multiday dynamics (rho = 0.73–0.80), while water level was most important for diurnal dynamics during both the growing and dormancy phenoperiods (rho = 0.72 and 0.56, respectively). Lags for the top‐ranked variables (i.e., gross primary productivity, dissolved oxygen, temperature, water level) occurred between 1 and 5 weeks at the seasonal scale and 1–24 hr at the diurnal scale. The EDM had high prediction capabilities for intra‐/inter‐seasonal patterns and annual CH 4 sums but had limitations in representing large, infrequent fluxes. Results highlight the importance of non‐linearity, drivers, lag times, and interconnections among multiple biophysical variables that regulate CH 4 fluxes in tidal wetlands. This research introduces a novel approach to examining CH 4 fluxes, which will aid in evaluating current paradigms in wetlands and other ecosystems.

Environmental Sciences & Ecology↗

Author Correction: US oil and gas system emissions from nearly one million aerial site measurements

Correction to: Naturehttps://doi.org/10.1038/s41586-024-07117-5 Published online 13 March 2024 In the version of the article initially published, several errors were present and have been corrected in the HTML and PDF versions of the article and Supplementary Information. The main results, conclusions, and our interpretations of the data remain unchanged. See the new Supplementary Information Section S15 for a more detailed description of the errors corrected and the resulting effects on the analysis. Data processing and methods corrections Overflight count correction: We previously used pre-computed source coverage data for some Carbon Mapper campaigns that was computed differently than was required for our analysis. We have re-computed Carbon Mapper source coverage based on flightline polygons and source coordinates. Transition point computation, well sites: The updated version now correctly compares the cumulative emissions distribution of simulated well site emissions with that of aerially detected sources (rather than plumes) when computing the transition point. Transition point computation, midstream: Additionally, the transition point calculation has been corrected to exclude aerially detected midstream emissions below the transition point, which was previously leading to double counting of these emissions. This error was not present for upstream (well site) emissions. Calculation errors Unit error: We corrected a specific unit conversion error affecting well site emissions in the Kairos Fort Worth dataset. Across all datasets, we also correct the conversion factor for converting from standard volume to mass for midstream emissions. Sorting error: We correct code that was applying incorrect sorting when computing correction factors to account for partial detection at well sites. Small typographical corrections were made in Fig. 1b and SI Section S4.1. Data processing and methods corrections Overflight count correction: We previously used pre-computed source coverage data for some Carbon Mapper campaigns that was computed differently than was required for our analysis. We have re-computed Carbon Mapper source coverage based on flightline polygons and source coordinates. Transition point computation, well sites: The updated version now correctly compares the cumulative emissions distribution of simulated well site emissions with that of aerially detected sources (rather than plumes) when computing the transition point. Transition point computation, midstream: Additionally, the transition point calculation has been corrected to exclude aerially detected midstream emissions below the transition point, which was previously leading to double counting of these emissions. This error was not present for upstream (well site) emissions. Calculation errors Unit error: We corrected a specific unit conversion error affecting well site emissions in the Kairos Fort Worth dataset. Across all datasets, we also correct the conversion factor for converting from standard volume to mass for midstream emissions. Sorting error: We correct code that was applying incorrect sorting when computing correction factors to account for partial detection at well sites. Small typographical corrections were made in Fig. 1b and SI Section S4.1. The following practices may help researchers conducting similar analyses avoid making similar errors: 1, Clear, accessible documentation explaining the interpretation of all columns in data input tables and all internal variables within the model, 2, Simple cross-check calculations computed before and after unit conversions.

Sherwin, Evan D↗

Simultaneous isotopic analysis of fission product Sr, Mo, and Ru in spent nuclear fuel particles by resonance ionization mass spectrometry

Abstract Fission product Sr, Mo, and Ru isotopes in six 10-μm particles of spent fuel from a pressurized water reactor were analyzed by resonance ionization mass spectrometry (RIMS) and evaluated for utility in nuclear material characterization. Previous measurements on these same samples showed widely varying U, Pu, and Am isotopic compositions owing to the samples’ differing irradiation environments within the reactor. This is also seen in Mo and Ru isotopes, which have the added complication of exsolution from the UO 2 fuel matrix. This variability is a hindrance to interpreting data from a collection of particles with incomplete provenance since it is not always possible to assign particles to the same batch of fuel based on isotopic analyses alone. In contrast, the measured 90 Sr/ 88 Sr ratios were indistinguishable across all samples. Strontium isotopic analysis can therefore be used to connect samples with otherwise disparate isotopic compositions, allowing them to be grouped appropriately for interpretation. Strontium isotopic analysis also provides a robust chronometer for determining the time since fuel irradiation. Because of the very high sensitivity of RIMS, only a small fraction of material in each of the 10 μm samples was consumed, leaving the vast majority still available for other analyses.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Case study of a bore wind-ramp event from lidar measurements and HRRR simulations over ARM Southern Great Plains

The rapid change of wind speed and direction on 21 August 2017 is studied using Doppler lidar measurements at five sites of the Atmospheric Radiation Measurement (ARM) Southern Great Plains (SGP) facility in north-central Oklahoma. The Doppler lidar data were investigated along with meteorological variables such as temperature, humidity, and turbulence available from the large suite of instrumentation deployed at the SGP Central Facility (C1) during the Land-Atmosphere Feedback Experiment in August 2017. Lidar measurements at five sites, separated by 55-70 km, allowed us to document the development and evolution of the wind flow over the SGP area, examine synoptic conditions to understand the mechanism that leads to the ramp event, and estimate the ability of the High-Resolution Rapid Refresh model to reproduce this event. The flow feature in question is an atmospheric bore, a small-scale phenomenon that is challenging to represent in models, that was generated by a thunderstorm outflow northwest of the ARM SGP area. The small-scale nature of bores, its impact on power generation, and the modeling challenges associated with representing bores are discussed in this paper. In conclusion, the results also provide information about model errors between sites of different surface and vegetation types.

54 ENVIRONMENTAL SCIENCES↗

Modeling of the metal–insulator transition temperature in alio-valently doped VO 2 through symbolic regression

The correlated semiconductor vanadium dioxide (VO 2 ) exhibits an insulator–metal transition (IMT) near room temperature, which is of interest in various device applications. Precise IMT temperature control is crucial to determine the use cases across technologies such as thermochromic windows, actuators for robots or neuronal oscillators. Doping the cation or anion sites can modulate the IMT by several tens of degrees and control hysteresis. However, modeling the effects of control parameters (e.g., doping concentration, type of dopants) is challenging due to complex experimental procedures and limited data, hindering the use of traditional data-driven machine learning approaches. Symbolic regression (SR) can bridge this gap by identifying nonlinear expressions connecting key input parameters to target properties, even with small data sets. In this work, we develop SR models to capture the IMT trends in VO 2 influenced by different dopant parameters. Using experimental data from the literature, our study reveals a dual nature of the IMT temperature with varying tungsten (W) doping concentrations. The symbolic model captures data trends and accounts for experimental variability, providing a complementary approach to first-principles calculations. Our feature-driven analysis across a broader class of dopants informs selectivity and provides qualitative insights into tuning phase transition properties valuable for neuromorphic computing and thermochromic windows.

36 MATERIALS SCIENCE↗

Multiple giant eruptions and X-ray emission in the recoiling AGN/LBV candidate SDSS1133

We present a comprehensive analysis of 20 yr worth of multicolour photometric light curves, multiepoch optical spectra, and X-ray data of an off-nuclear variable object SDSS1133 in Mrk 177 at z = 0.0079. The UV-optical light curves reveal that SDSS1133 experienced four outbursts in 2001, 2014, 2019, and 2021. The persistent UV-optical luminosity in the non-outbursting state is ~1041 erg s -1 with small-scale flux variations, and peak luminosities during the outbursts reach ~10 42 erg s -1 . The optical spectra exhibit enduring broad hydrogen Balmer P-Cygni profiles with the absorption minimum at ~-2000 km s -1 , indicating the presence of fast-moving ejecta. Chandra detected weak X-ray emission at a 0.3-10-keV luminosity of L X = 4 × 10 38 erg s -1 after the 2019 outburst. These lines of evidence suggests that SDSS1133 is an extreme luminous blue variable (LBV) star experiencing multiple giant eruptions with interactions of the ejected shell with different shells and/or circumstellar medium (CSM), and disfavours the recoiling active galactic nuclei scenario suggested in the literature. We suggest that pulsational pair-instability may provide a viable explanation for the multiple energetic eruptions in SDSS1133. If the current activity of SDSS1133 is a precursor of a supernova explosion, we may be able to observe a few additional giant eruptions and then the terminal supernova explosion or collapse to a massive black hole in future observations.

79 ASTRONOMY AND ASTROPHYSICS↗

TCAD-Machine Learning Enabled TID Compact Model Development for Commercial SiC MOSFET

We propose a TCAD (Technology Computer Aided Design)-machine learning coupled approach that combines a TCAD tool (Charon), optimization/uncertainty quantification tool (Dakota), surrogate models, and Bayesian learning capabilities. The coupling approach is used for accurate modeling and calibration of total ionizing dose (TID) induced threshold voltage (V th ) shifts in Commercial-Off-The-Shelf (COTS) semiconductor devices and to develop physics-informed TID compact models. This versatile approach is applied to model the TID effect in an exemplar COTS 3.3 kV SiC power MOSFET (Metal-Oxide-Semiconductor Field-Effect Transistor). With the Charon-Dakota coupling, we can determine key device geometry and doping values based on device physics, which are difficult to obtain or not available for COTS devices but important for TCAD simulation; additionally, we can efficiently generate thousands of simulation results in a large parameter space, which makes it possible to develop data-driven surrogate models and perform Bayesian calibration. Utilizing the full tool-coupling approach, we achieve calibrated TCAD simulation models that accurately capture the average TID-induced V th shifts behavior with total doses and V th shifts saturation at high doses as observed in experimental data. More importantly, the calibrated TCAD simulations are obtained with determined TID model parameters (e.g., hole trap density and capture cross section) values that contain well quantified uncertainties. Furthermore, we can isolate and quantify the noises that are not captured by the TCAD models but exist in the measured data due to measurements and devices variabilities. Lastly, the calibrated surrogate models are used to develop physics-informed TID compact models. The method is generalizable to other devices and/or radiation conditions with few modifications and can provide well-determined uncertainties.

COTS↗

pnnl/Pathway_Controlled_Optimization

A method for prediction of cell regulation to maximize cell growth rate while maintaining the solvent capacity of the cell. Prediction is formulated as an optimization problem using a thermodynamic framework that can leverage experimental data. We develop a formulation and variable initialization procedure that allows for computing solutions of the optimization with an interior point method

Central, PNNL Developer↗