Search NASA⌕ Search

SEARCH · Search NASA

Results for “Occupation number”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Impact of microkinetic modeling assumptions on predicted kinetics and mechanisms over undercoordinated sites

Accurate modeling of catalytic reactions on undercoordinated sites requires accounting for the structural and ensemble-specific nature of the active sites. This study examines how common microkinetic modeling (MKM) assumptions affect predicted kinetics and mechanisms on the stepped Pt(211) facet for the ethane dehydrogenation (EDH) and the ethane hydrogenolysis (EH). Six (211) MKMs were developed, differing in (i) the number of active sites represented, (ii) adsorbate site occupancy treatment, and (iii) inclusion of cross-facet interactions. These models are benchmarked against a particle-based microkinetic model (PB-MKM), which best represents step-edge behavior. MKM assumptions caused deviations in turnover frequencies exceeding ten orders of magnitude and led to contrasting mechanistic and selectivity predictions. Multi-site MKMs overestimate activity by inflating free site availability, single-site models underestimate activity, and uniform occupancy models overpredict coverage of multi-dentate intermediates, leading to reaction-specific artifacts. Overall, the Combined Site Edge Model (CSEM), a single-site MKM accounting for site occupancy and cross-facet interactions, most closely approximates PB-MKM predictions. All models predict similar kinetics when surfaces are clean or primarily occupied by monodentate species. This work provides practical guidance for selecting MKM frameworks for undercoordinated catalytic surfaces and highlights the critical role of modeling assumptions in catalytic predictions.

(211) facet↗
DOE OSTI2025

Readout electronics for low occupancy High-Pressure Gas TPCs

High-Pressure Gas Time Projection Chambers (HPgTPCs) have benefits such as low energy thresholds, magnetisability, and 4π acceptance, making them ideal for neutrino experiments such as DUNE. We present the design of an FPGA-based solution optimised for Gaseous Argon Near Detector (ND-GAr), which is part of the Phase-II more capable near detector for DUNE. These electronics reduce the cost significantly compared to using collider readout electronics, which are typically designed for much higher occupancy and therefore, for example, need much larger numbers of FPGAs and power per channel. We demonstrate the performance of our electronics with the Teststand for an Overpressurised Argon Detector (TOAD) at Fermilab in the US at a range of pressures and gas mixtures up to 4.5 barA, reading out ∼10 000 channels from a Multi-Wire Proportional Chamber (MWPC). The operation took place between April and July of 2024. We measure the noise characteristics of the system to be sufficiently low, and we identify sources of noise that can be further mitigated in the next iteration. We also note that the cooling scheme used in the test requires improvement before full-scale deployment. Despite these necessary improvements, we show that the system can fulfil the needs of a HPgTPC for a fraction of the price of collider readout electronics.

Data acquisition concepts↗
DOE OSTI2020

The Mertens Unrolled Network (MU-Net): A High Dynamic Range Fusion Neural Network for Through the Windshield Driver Recognition

Face recognition of vehicle occupants through windshields in unconstrained environments poses a number of unique challenges ranging from glare, poor illumination, driver pose and motion blur. In this paper, we further develop the hardware and software components of a custom vehicle imaging system to better overcome these challenges. After the build out of a physical prototype system that performs High Dynamic Range (HDR) imaging, we collect a small dataset of through-windshield image captures of known drivers. We then reformulate the classical Mertens-Kautz-Van Reeth HDR fusion algorithm as a pre-initialized neural network, which we name the Mertens Unrolled Network (MU-Net), for the purpose of fine-tuning the HDR output of through-windshield images. Reconstructed faces from this novel HDR method are then evaluated and compared against other traditional and experimental HDR methods in a pre-trained state-of-the-art (SOTA) facial recognition pipeline, verifying the efficacy of our approach.

Ruby, Max↗
DOE OSTI2022

Driving chemical reactions with polariton condensates

Abstract When molecular transitions strongly couple to photon modes, they form hybrid light-matter modes called polaritons. Collective vibrational strong coupling is a promising avenue for control of chemistry, but this can be deterred by the large number of quasi-degenerate dark modes. The macroscopic occupation of a single polariton mode by excitations, as observed in Bose-Einstein condensation, offers promise for overcoming this issue. Here we theoretically investigate the effect of vibrational polariton condensation on the kinetics of electron transfer processes. Compared with excitation with infrared laser sources, the vibrational polariton condensate changes the reaction yield significantly at room temperature due to additional channels with reduced activation barriers resulting from the large accumulation of energy in the lower polariton, and the many modes available for energy redistribution during the reaction. Our results offer tantalizing opportunities to use condensates for driving chemical reactions, kinetically bypassing usual constraints of fast intramolecular vibrational redistribution in condensed phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Hardware-Based Emulator with Deep Learning Model for Building Energy Control and Prediction Based on Occupancy Sensors’ Data

Heating, ventilation, and air conditioning (HVAC) is the largest source of residential energy consumption. Occupancy sensors’ data can be used for HVAC control since it indicates the number of people in the building. HVAC and sensors form a typical cyber-physical system (CPS). In this paper, we aim to build a hardware-based emulation platform to study the occupancy data’s features, which can be further extracted by using machine learning models. In particular, we propose two hardware-based emulators to investigate the use of wired/wireless communication interfaces for occupancy sensor-based building CPS control, and the use of deep learning to predict the building energy consumption with the sensor data. We hypothesize is that the building energy consumption may be predicted by using the occupancy data collected by the sensors, and question what type of prediction model should be used to accurately predict the energy load. Another hypothesis is that an in-lab hardware/software platform could be built to emulate the occupancy sensing process. The machine learning algorithms can then be used to analyze the energy load based on the sensing data. To test the emulator, the occupancy data from the sensors is used to predict energy consumption. The synchronization scheme between sensors and the HVAC server will be discussed. We have built two hardware/software emulation platforms to investigate the sensor/HVAC integration strategies, and used an enhanced deep learning model—which has sequence-to-sequence long short-term memory (Seq2Seq LSTM)—with an attention model to predict the building energy consumption with the preservation of the intrinsic patterns. Because the long-range temporal dependencies are captured, the Seq2Seq models may provide a higher accuracy by using LSTM architectures with encoder and decoder. Meanwhile, LSTMs can capture the temporal and spatial patterns of time series data. The attention model can highlight the most relevant input information in the energy prediction by allocating the attention weights. The communication overhead between the sensors and the HVAC control server can also be alleviated via the attention mechanism, which can automatically ignore the irrelevant information and amplify the relevant information during CNN training. Our experiments and performance analysis show that, compared with the traditional LSTM neural network, the performance of the proposed method has a 30% higher prediction accuracy.

Ye, Zhijing↗
DOE OSTI2020

A Rapid Population Assessment Method for Wild Pigs Using Baited Cameras at 3 Study Sites

ABSTRACT Reliable and efficient population estimates are a critical need for effective management of invasive wild pigs ( Sus scrofa ). We evaluated the use of 10‐day camera grids for rapid population assessment (RPA) of wild pigs at 3 study sites that varied in vegetation communities and wild pig densities. Study areas included Buck Island Ranch, Florida; Tejon Ranch, California; and the Savannah River Site, South Carolina, USA, during 2016–2018. Rapid population assessments grids were composed of baited camera traps spaced approximately 500 or 750 m apart. Two RPA grids were deployed per study site and each grid was deployed twice (4–6 months apart) to assess changes in response to season or population control efforts. We assessed the ability of RPA grids to track population trends, how camera number influenced estimate precision, and how relative abundance indices related to density estimates. We detected changes in occupancy probability, detection probability, and N‐mixture estimates following removal operations and between seasons, but the ability of RPA grids to track population trends was dependent on the statistical method used and number of cameras traps. Increasing the number of cameras traps used in RPA grids increased precision, and these results can be used in determining survey design and estimate choice. We found that estimates of occupancy probability, detection probability, and N‐mixture estimates were positively correlated with spatially explicit capture–recapture density estimates. Thus, these less labor‐intensive estimates from RPA grids showed potential to index the relative abundance of wild pigs in some systems. Our evaluation of RPAs indicates that using study‐specific combinations of statistical method and number of cameras can provide a useful tool for monitoring wild pig presence, tracking population trends, and evaluating the effectiveness of management actions. © 2020 The Wildlife Society.

Schlichting, Peter E.↗
DOE OSTI2025

Optical galaxy cluster mock catalogs with realistic projection effects: Validations with the SDSS clusters

Galaxy clusters identified in optical imaging surveys suffer from projection effects: Physically unassociated galaxies along a cluster’s line of sight can be counted as its members and boost the observed richness (the number of cluster members). To model the impact of projection on cluster cosmology analyses, we apply a halo occupation distribution model to 𝑁-body simulations to simulate the red galaxies contributing to cluster members, and we use the number of galaxies in a cylinder along the line of sight (counts in cylinders) to model the impact of projection on cluster richness. We compare three projection models: uniform, quadratic, and Gaussian, and we convert between them by matching their effective cylinder volumes. We validate our mock catalogs using SDSS redMaPPer clusters’ data vectors, including counts vs richness, stacked lensing signal, spectroscopic redshift distribution of member galaxies, and richness remeasured on a redshift grid. We find the former two are insensitive to the projection model, while the latter two favor a quadratic projection model with a width of ≈180 ℎ −1 Mpc (equivalent to the volume of a uniform model with a width of 100 ℎ −1 Mpc and a Gaussian model with a width of 110 ℎ −1 Mpc, or a Gaussian redshift error of 0.04). Furthermore, our framework provides an efficient and flexible way to model optical cluster data vectors, paving the way for a simulation-based joint analysis for clusters, galaxies, and shear.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Consumer safety-oriented scheduling of rotating power outages during heat waves

Extreme heat events have widespread effects on power systems, reducing available generation capacity, limiting transmission capabilities, and causing unusual demand patterns on the consumer side. As these combined effects expose bulk transmission systems to potential large-scale blackouts, utilities may be required to schedule and apply rotating outages, by temporarily and alternately disconnecting distribution substations to reduce overload. However, utilities lack mechanisms to inform these events, exacerbating the negative effects of heat waves on affected communities. This paper introduces a novel framework for scheduling rotating outages during heat waves while considering impacts on consumers’ safety. Instead of random sequential load shedding, we propose a methodology to rotate power outages considering a metric that quantifies the indoor overheating risk of groups of consumers during a power outage. The overheating risk is derived from a detailed building simulation using CityBES, where the buildings are modeled based on available data—use type, year built, floor area, number of stories, location—while presence of air conditioning and occupancy are calibrated from smart meter data. Based on the metric, an algorithm to schedule the rotating outages is applied to prioritize feeders for disconnection at each hour according to their overheating risk to meet a utility load reduction target. Applied to two substations and seven feeders in the Portland General Electric territory, the results show that this approach effectively leads to the lowest overheating risk during the resulting outage schedules, with an average 10.1% lower overheating compared to uninformed schedules.

Building thermal simulation↗
NASA NTRS1975

Results of investigations on a 0.010-scale 140A/B configuration space shuttle vehicle orbiter model 72-0 in the NASA/Langley Research Center continuous flow hypersonic tunnel (OA90)

Data are documented which were obtained during wind tunnel tests. The test was conducted beginning 4 March and ending 6 March 1974 for a total of 24 occupancy hours. all test runs were conducted at a Mach number of 10.3 and at Reynolds numbers of 0.65, 1.0 and 1.33 million per foot. Only the complete 140A/B was tested with various elevon, speedbrake, and bodyflap settings at angles of attack from 12 to 37 degrees at 0 and -5 degrees of beta, and from 0 to -9 degrees of beta at 20 and 30 degrees angle of attack. The purpose was to obtain hypersonic longitudinal and lateral-directional stability and control characteristics of the updated space shuttle vehicle configuration.

Hawthorne, P. J.↗
NASA NTRS1984

Ratioed scatter diagrams - An erotetic method for phase identification on complex surfaces using scanning Auger microscopy

By ratioing multiple Auger intensities and plotting a two-dimensional occupational scatter diagram while digitally scanning across an area, the number and elemental association of surface phases can be determined. This can prove a useful tool in scanning Auger microscopic analysis of complex materials. The technique is illustrated by results from an anomalous region on the reaction zone of a SiC/Ti-6Al-4V metal matrix composite material. The anomalous region is shown to be a single phase associated with sulphur and phosphorus impurities. Imaging of a selected phase from the ratioed scatter diagram is possible and may be a useful technique for presenting multiple scanning Auger images.

Browning, R.↗
NASA NTRSDate not supplied

Soyuz Landing Risk Characterization

INTRODUCTION United States On-orbit Segment (USOS) astronauts have been returning to Earth from the International Space Station (ISS) aboard the Russian Soyuz vehicle since 2003. The energetics associated with Soyuz landings are comparable to our next generation of US space vehicles (Orion, Crew Dragon, and Starliner). Soyuz also lands crew in a similar state of spaceflight deconditioning that is anticipated using the future vehicles. A number of injuries have now been observed during these Soyuz landings. Currently it is unknown how Soyuz landing accelerations and the numbers and types of associated injuries relate to the new occupant protection requirements levied upon future space vehicles. Understanding this relationship will allow better quantification of the risk of injury for future spacecraft designs. METHODS An estimate of the occurrences of injury during Soyuz landings has been determined using data contained in NASA flight medicine databases and supplemented with data collected from crewmembers and flight surgeons. At the time of this abstract, 96 USOS astronauts have returned to Earth in the Soyuz (59 US, 31 International Partner, and 6 spaceflight participants). Of that total, data from 80 individual crew landings has been collected through this study. Injuries are classified as either contusions/abrasions, Class I (minor, no medical follow-up), Class II (moderate, medical follow-up necessary), Class III (severe), and Class IV (life threatening). Current NASA occupant protection standards are primarily based on the Multi-axial Dynamic Response Index (MDRI), which is a simple lumped-parameter spring, mass, damper model tuned to human impact responses in three orthogonal axes. RESULTS Using what is known about Soyuz landing dynamics from airborne and drop test data, the MDRI predicts essentially no Class IV or III injuries, < 1% Class II injuries, and < 5% Class I injuries. Approximately one-third of all USOS crewmembers for whom data has been gathered have suffered some sort of injury related to landing in the Soyuz vehicle. Most of these injuries fall into the contusion/abrasion category (21.3 %). Class I injuries have been sustained by 5.0% of all crew, and Class II injuries have been observed in 3.8%. No Class III or IV injuries have been sustained to date. Forty-three injuries have been documented, with some crewmembers sustaining more than one injury in a single landing. The knee was the most likely area of injury (n=9), followed by the back (n=8), and then the arm (n=7). CONCLUSION Soyuz landing dynamics are the most comparable analog environment for the anticipated loads associated with Orion and commercial crew vehicle landings. The MDRI under predicts the percentage of Class II injuries experienced during Soyuz landings. The MDRI is better at predicting Class I injury occurrences. However, if contusions/abrasions are included in the minor injury Class I category, then the MDRI also vastly under predicts those injuries as well. Given this data, it will be important to re-evaluate the expected injury rates for future vehicles, and work toward improving the predictive tools for spaceflight use. Spaceflight deconditioning may account for some of the under prediction, and work is ongoing to assess the relationship between landing injuries and impact tolerance changes due to spaceflight deconditioning.

N Newby↗
NASA NTRSDate not supplied

Soyuz Landing Risk Characterization

INTRODUCTION United States On-orbit Segment (USOS) astronauts have been returning to Earth from the International Space Station (ISS) aboard the Russian Soyuz vehicle since 2003. The energetics associated with Soyuz landings are comparable to our next generation of US space vehicles (Orion, Crew Dragon, and Starliner). Soyuz also lands crew in a similar state of spaceflight deconditioning that is anticipated using the future vehicles. A number of injuries have now been observed during these Soyuz landings. Currently it is unknown how Soyuz landing accelerations and the numbers and types of associated injuries relate to the new occupant protection requirements levied upon future space vehicles. Understanding this relationship will allow better quantification of the risk of injury for future spacecraft designs. METHODS An estimate of injury occurrence during Soyuz landings has been determined using data contained in NASA flight medicine databases and supplemented with data collected from crewmembers and flight surgeons. At the time of this abstract, 96 USOS astronauts have returned to Earth in the Soyuz (59 US, 31 International Partner, and 6 spaceflight participants). Of that total, data from 80 individual crew landings has been collected through this study as of 2021. Injuries are classified either as contusions/abrasions, Class I (minor, no medical follow-up), Class II (moderate, medical follow-up necessary), Class III (severe), or Class IV (life threatening). Current NASA occupant protection standards are primarily based on the Multi-axial Dynamic Response Index (MDRI), which is a simple lumped-parameter spring, mass, damper model tuned to human impact responses in three orthogonal axes. RESULTS Using what is known about Soyuz landing dynamics from airborne and drop test data, the MDRI predicts essentially no Class IV or III injuries, < 1% Class II injuries, and < 5% Class I injuries. Approximately one-third of all USOS crewmembers for whom data has been gathered have suffered some sort of injury related to landing in the Soyuz vehicle. Most of these injuries fall into the contusion/abrasion category (21.3 %) (n.b. This is the percent for whom contusion/abrasion was the worst injury. Those with class I or II injuries typically also received contusions/abrasions). Class I injuries have been sustained by 5.0% of all crew, and Class II injuries have been observed in 3.8%. No Class III or IV injuries have been sustained to date. Forty-three injuries have been documented, with some crewmembers sustaining more than one injury in a single landing. The knee was the most likely area of injury (n=9), followed by the back (n=8), then the arm (n=7). CONCLUSION Soyuz landing dynamics are the most comparable analog environment for the anticipated loads associated with Orion and commercial crew vehicle landings. The MDRI under predicts the percentage of Class II injuries experienced during Soyuz landings, but it is better at predicting Class I injury occurrences. However, if contusions/abrasions are included in the minor injury Class I category, then the MDRI vastly under predicts those injuries as well. Given this data, it is important to re-evaluate the expected injury rates for future vehicles and work toward improving the predictive tools for spaceflight use. Spaceflight deconditioning may account for some of the under prediction, and work is ongoing to assess the relationship between landing injuries and impact tolerance changes due to spaceflight deconditioning. Future work includes expanding this study to involve private space missions on new vehicles to better characterize the effects of time in flight, suit and seat design, and vehicle dynamics.

N Newby↗
NASA NTRSDate not supplied

Soyuz Landing Risk Characterization

INTRODUCTION United States On-orbit Segment (USOS) astronauts have been returning to Earth from the International Space Station (ISS) aboard the Russian Soyuz vehicle since 2003. The energetics associated with Soyuz landings are comparable to our next generation of US space vehicles (Orion, Crew Dragon, and Starliner). Soyuz also lands crew in a similar state of spaceflight deconditioning that is anticipated using the future vehicles. A number of injuries have now been observed during these Soyuz landings. Currently it is unknown how Soyuz landing accelerations and the numbers and types of associated injuries relate to the new occupant protection requirements levied upon future space vehicles. Understanding this relationship will allow better quantification of the risk of injury for future spacecraft designs. METHODS An estimate of injury occurrence during Soyuz landings has been determined using data contained in NASA flight medicine databases and supplemented with data collected from crew members and flight surgeons. At the time of this abstract, 96 USOS astronauts have returned to Earth in the Soyuz (59 US, 31 International Partner, and 6 spaceflight participants). Of that total, data from 80individual crew landings has been collected through this study as of September 2023. Injuries are classified either as contusions/abrasions, Class I (minor, no medical follow-up), Class II (moderate, medical follow-up necessary), Class III (severe), or Class IV (life threatening). Current NASA occupant protection standards are primarily based on the Multi-axial Dynamic Response Index (MDRI), which is a simple lumped-parameter spring, mass, damper model tuned to human impact responses in three orthogonal axes. RESULTS Using what is known about Soyuz landing dynamics from airborne and drop test data, the MDRI predicts essentially no Class IV or III injuries, < 1% Class II injuries, and < 5% Class I injuries. Approximately one-third of all USOS crewmembers for whom data has been gathered have suffered some sort of injury related to landing in the Soyuz vehicle. Most of these injuries fall into the contusion/abrasion category (21.3%) (n.b. This is the percent for whom contusion/abrasion was the worst injury. Those with class I or II injuries typically also received contusions/abrasions). Class I injuries have been sustained by 5.0% of all crew, and Class II injuries have been observed in 3.8%. No Class III or IV injuries have been sustained to date. Forty-three injuries have been documented, with some crewmembers sustaining more than one injury in a single landing. The knee was the most likely area of injury (n=9), followed by the back (n=8), then the arm (n=7). CONCLUSION Soyuz landing dynamics are the most comparable analog environment for the anticipated loads associated with Orion and commercial crew vehicle landings. The MDRI under predicts the percentage of Class II injuries experienced during Soyuz landings, but it is better at predicting Class I injury occurrences. However, if contusions/abrasions are included in the minor injury Class I category, then the MDRI vastly under predicts those injuries as well. Given this data, it is important to re-evaluate the expected injury rates for future vehicles and work toward improving the predictive tools for spaceflight use. Spaceflight deconditioning may account for some of the under prediction, and work is ongoing to assess the relationship between landing injuries and impact tolerance changes due to spaceflight deconditioning. Future work includes expanding this study to involve private space missions on new vehicles to better characterize the effects of time in flight, suit and seat design, and vehicle dynamics.

N Newby↗
NASA NTRSDate not supplied

Soyuz Landing Risk Characterization

INTRODUCTION United States On-orbit Segment (USOS) astronauts have been returning to Earth from the International Space Station (ISS) aboard the Russian Soyuz vehicle since 2003. The energetics associated with Soyuz landings are comparable to our next generation of US space vehicles (Orion, Crew Dragon, and Starliner). Soyuz also lands crew in a similar state of spaceflight deconditioning that is anticipated using the future vehicles. A number of injuries have now been observed during these Soyuz landings. Currently it is unknown how Soyuz landing accelerations and the numbers and types of associated injuries relate to the new occupant protection requirements levied upon future space vehicles. Understanding this relationship will allow better quantification of the risk of injury for future spacecraft designs. METHODS An estimate of injury occurrence during Soyuz landings has been determined using data contained in NASA flight medicine databases and supplemented with data collected from crewmembers and flight surgeons. At the time of this abstract, 96 USOS astronauts have returned to Earth in the Soyuz (59 US, 31 International Partner, and 6 spaceflight participants). Of that total, data from 80 individual crew landings has been collected through this study as of September 2023. Injuries are classified either as contusions/abrasions, Class I (minor, no medical follow-up), Class II (moderate, medical follow-up necessary), Class III (severe), or Class IV (life threatening). Current NASA occupant protection standards are primarily based on the Multi-axial Dynamic Response Index (MDRI), which is a simple lumped-parameter spring, mass, damper model tuned to human impact responses in three orthogonal axes. RESULTS Using what is known about Soyuz landing dynamics from airborne and drop test data, the MDRI predicts essentially no Class IV or III injuries, < 1% Class II injuries, and < 5% Class I injuries. Approximately one-third of all USOS crewmembers for whom data has been gathered have suffered some sort of injury related to landing in the Soyuz vehicle. Most of these injuries fall into the contusion/abrasion category (21.3 %) (n.b. This is the percent for whom contusion/abrasion was the worst injury. Those with class I or II injuries typically also received contusions/abrasions). Class I injuries have been sustained by 5.0% of all crew, and Class II injuries have been observed in 3.8%. No Class III or IV injuries have been sustained to date. Forty-three injuries have been documented, with some crewmembers sustaining more than one injury in a single landing. The knee was the most likely area of injury (n=9), followed by the back (n=8), then the arm (n=7). CONCLUSION Soyuz landing dynamics are the most comparable analog environment for the anticipated loads associated with Orion and commercial crew vehicle landings. The MDRI under predicts the percentage of Class II injuries experienced during Soyuz landings, but it is better at predicting Class I injury occurrences. However, if contusions/abrasions are included in the minor injury Class I category, then the MDRI vastly under predicts those injuries as well. Given this data, it is important to re-evaluate the expected injury rates for future vehicles and work toward improving the predictive tools for spaceflight use. Spaceflight deconditioning may account for some of the under prediction, and work is ongoing to assess the relationship between landing injuries and impact tolerance changes due to spaceflight deconditioning. Future work includes expanding this study to involve private space missions on new vehicles to better characterize the effects of time in flight, suit and seat design, and vehicle dynamics.

P Greenhalgh↗
DOE OSTI2021

Probing Multiconfigurational States by Spectroscopy: The Cerium XAS L 3 ‐edge Puzzle

Abstract The Ce L 3 edge XAS spectra of CeO 2 and cerocene [Ce(C 8 H 8 ) 2 ] were calculated with relativistic ab‐initio multireference wavefunction approaches capable of reproducing the observed spectra accurately. The study aims to resolve the decades‐long puzzle regarding the relationship between the number and relative intensities of the XAS peaks and the 4f electron occupation in the ground state (GS) versus the core‐excited states (ESs). CeO 2 and cerocene exemplify the different roles of covalent bonding and wavefunction configurational composition in the observed intensity patterns. Good agreement is found between the calculated GS 4f‐shell occupations and the value derived from XAS measurements using peak areas ( n f ). The identity of the two‐peaked Ce L 3 edge is fully rationalized from the perspective of the relaxed wavefunctions for the GS and core ESs. The states underlying the different peaks differ from each other in a surprisingly simple way that can be associated with 4f 1 vs. 4f 0 sub‐configurations. Furthermore, part of one of the cerocene spectral peaks is associated with 4f 2 sub‐configurations. The pattern therefore reveals excited states that can be interpreted in terms of Ce IV and III oxidation numbers, as long assumed, with Ce II states additionally appearing in the cerocene spectrum. While this work demonstrates the rough accuracy of the conventional approach to determining n f from Ce L 3 ‐edge XAS, limitations are highlighted in terms of the ultimate accuracy of this approach and the potential of observing new types of excited states. The need to determine the sources of n f by calculations, is stressed.

Sergentu, Dumitru‐Claudiu↗
DOE OSTI2023

DESI mock challenge: Halo and galaxy catalogues with the bias assignment method

We present a novel approach to the construction of mock galaxy catalogues for large-scale structure analysis based on the distribution of dark matter halos obtained with effective bias models at the field level. We aim to produce mock galaxy catalogues capable of generating accurate covariance matrices for a number of cosmological probes that are expected to be measured in current and forthcoming galaxy redshift surveys (e.g. two- and three-point statistics). The construction of the catalogues shown in this paper is part of a mock-comparison project within the Dark Energy Spectroscopic Instrument (DESI) collaboration. We use the bias assignment method ( BAM ) to model the statistics of halo distribution through a learning algorithm using a few detailed N-body simulations, and approximated gravity solvers based on Lagrangian perturbation theory. We introduce cosmic-web-dependent corrections to modelling redshift-space distortions at the N-body level – both in the halo and galaxy distributions –, as well as a multi-scale approach for accurate assignment of halo properties. Using specific models of halo occupation distributions to populate halos, we generate galaxy mocks with the expected number density and central-satellite fraction of emission-line galaxies, which are a key target of the DESI experiment. BAM generates mock catalogues with per cent accuracy in a number of summary statistics, such as the abundance, the two- and three-point statistics of halo distributions, both in real and redshift space. In particular, the mock galaxy catalogues display ~3%-10% accuracy in the multipoles of the power spectrum up to scales of k ~ 0.4 h -1 Mpc. We show that covariance matrices of two- and three-point statistics obtained with BAM display a similar structure to the reference simulation. BAM offers an efficient way to produce mock halo catalogues with accurate two- and three-point statistics and is able to generate a variety of multi-tracer catalogues with precise covariance matrices of several cosmological probes. We discuss future developments of the algorithm towards mock production in DESI and other galaxy-redshift surveys.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Sustainable Oxide Electrocatalyst for Hydrogen- and Oxygen-Evolution Reactions

In this work, an electrocatalyst for water splitting based on earth-abundant metals is reported. This perovskite-oxide catalyst, CaSrFe 0.75 Co 0.75 Mn 0.5 O 6-δ (CSFCM), is examined using both experimental and computational methods. It demonstrates a combination of properties, which include (a) very high activity for the oxygen-evolution reaction with an overpotential of eta = 0.19 V at 10 mA/cm 2 , (b) high stability over 1000 cycles of catalysis, (c) the ability to catalyze the hydrogen-evolution reaction effectively in both acidic and basic conditions, and (d) catalytic activity as a single-phase bulk material without the need for any additional processing, multicomponent composite preparation, or nanofabrication. Therefore, the catalytic activity of CSFCM is intrinsic, making it a good benchmark compound for future studies of electrocatalytic parameters. This work also highlights the impact of systematic structural design on electrocatalytic activity. Results from density functional theory calculations indicate that in addition to an optimal e g occupancy of similar to 1, an additional descriptor, i.e., maximizing the number of free e g carriers, correlates with the electrocatalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Reactions of Np(VI) and Pu(VI) with Phenanthroline Result in Bending the [NpVIO2]2+ Unit and a Reduced Pu(V) Species

Despite decades of actinyl chemistry, genuinely bent actinyl structures remain rare beyond uranium. We report the first crystallographic characterization of a bent neptunyl(VI) complex, NpO 2 Cl 2 (phen) 2, along with a linear plutonyl species that, unexpectedly, adopts the +V oxidation state. Coordination of two 1,10-phenanthroline ligands to NpO 2 2+ enforces pronounced bending of the O yl –Np–O yl unit to 162° through steric clashes with the axial phenathroline ligand, representing the sharpest angle reported for any neptunyl(VI) complex. In contrast, synthesis with PuO 2 2+ produces a reduced linear Pu(V) species, PuO 2 Cl(phen) 2, underscoring the redox lability and the reluctance of plutonium to distort. Raman and IR spectra yield the first experimental stretching and interaction force constants for plutonyl(V). Comparison with values for plutonyl(VI) and bent and linear uranyl(VI) and neptunyl(VI) compounds shows that reduction perturbs the actinyl bond more than bending within one oxidation state. Electrochemical and spectroscopic studies clarify phenanthroline binding to Pu(VI) and the system’s reactivity. Quantum chemical calculations indicate that bending is energetically favored in the U–Np–Pu series, but the stabilization energy decreases as the actinide atomic number increases. NBO and QTAIM analyses reveal systematic trends: increasing 5f occupancy and decreasing An–O yl bond covalency from U to Pu. These results demonstrate that ligand-induced bending in neptunyl(VI) species is not only electronically feasible but also synthetically achievable, though plutonyl(VI) is constrained by redox reactivity. This work expands the frontier of nonlinear actinyl chemistry and illuminates how structure, oxidation state, and electronic configuration interrelate across the actinyl series.

actinides↗