SEARCH · Engineering Papers

Results for “density estimation”

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.

SourceResearch connectionFrom yearThrough year

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

At least 955 records · Page 53

All sources NASA NTRS DOE OSTI

DOE OSTI2023

Weak Gravitational Lensing of Low Surface Brightness Galaxies in the Dark Energy Year 3 Catalog

We present galaxy-galaxy lensing measurements of a sample of low surface brightness galaxies (LSBGs) drawn from the Dark Energy Survey Year 3 (Y3) data. LSBGs are diffuse galaxies with a surface brightness dimmer than the ambient night sky. Given their faintness, the use of standard observational techniques proves challenging. Weak gravitational lensing probes both the baryonic and dark matter content of galaxies, rendering it a powerful technique to estimate LSBG masses. The LSBG lens sample consists of 23, 790 total extended galaxies separated into red and blue color types at $g-i\ge 0.60$ and $g-i\le 0.60$, respectively. We use the Y3 \sc{metacalibration} shape catalog as the source sample, with a number density of $5.59 \mathrm{gal}/\mathrm{arcmin}^2$. We measure the tangential shear around the lens galaxies across angular scales of $0.25-400$ arcmin and find a signal-to-noise of 6.67 for red galaxies, 2.17 for blue galaxies, and 5.30 for the total sample. We fit a model built from two NFW profiles corresponding to the LSBG dark matter subhalo and host halo to the red LSBG shear measurements with an MCMC. We estimate the host halo mass at $7.3 ^{+2.0}_{-1.6}\times 10^{12} M_\mathrm{\odot}$. We place a 95\% upper bound on the subhalo mass at $3\times 10^{11} M_\mathrm{\odot}$. We utilize the lens sample photometry to obtain an estimate of the red LSBG stellar mass distribution. We compare the ratio between the stellar mass and the subhalo mass to the parameterized, satellite-specific SHMR. This work represents the first example of an attempted constraint on the masses of LSBGs using weak gravitational lensing.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2023

Estimating Ocean Observation Impacts on Coupled Atmosphere‐Ocean Models Using Ensemble Forecast Sensitivity to Observation (EFSO)

Ensemble Forecast Sensitivity to Observation (EFSO) is a technique that can efficiently identify the beneficial/detrimental impacts of every observation in ensemble-based data assimilation (DA). While EFSO has been successfully employed on atmospheric DA, it has never been applied to ocean or coupled DA due to the lack of a suitable error norm for oceanic variables. This study introduces a new density-based error norm incorporating sea temperature and salinity forecast errors, making EFSO applicable to ocean DA for the first time. We implemented the oceanic EFSO on the CFSv2-LETKF and investigated the impact of ocean observations under a weakly coupled DA framework. By removing the detrimental ocean observations detected by EFSO, the CFSv2 forecasts were significantly improved, showing the validation of impact estimation and the great potential of EFSO to be extended as a data selection criterion.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Hanford Reach Fall Chinook Salmon Productivity Analysis, Brood Years 1975–2016

Updating the Hanford Reach fall Chinook salmon productivity analysis to include seven additional years of data (BY 2010–2016), including three years of record escapements (>150,000 adults), reaffirmed the highly productive nature of this population and the positive effect of flow fluctuation constraints as implemented at Priest Rapids Dam by the VBSA and HRFCPP. The addition of several years of high escapements also revealed that competition among juveniles (and not spawning habitat limitations) is likely the mechanism driving density dependence in the Hanford Reach. The addition of the high escapement brood years also provided evidence for the high recruitment capacity of the population. As such, the WDFW may consider increasing the maximum escapement goal from 42,000 adults to 49,000 adults, which would be more in-line with SMSY as estimated from this update. Given the in-river protections that are in place as part of the HRFCPP, ocean conditions appear to be the primary factor controlling adult production. Therefore, the success of any additional management actions taken in freshwater are likely to be dependent on survival in the ocean. As such, the most effective management actions may be those that limit juvenile competition and density dependent growth effects in the Hanford Reach. Limiting competition would be expected to increase growth, resulting in larger smolts that would be less likely to suffer size-dependent mortality in the marine environment, even during years of poor ocean conditions. Increasing terminal harvest rates when high escapements are anticipated (from downstream dam counts) is one management option that could help to curtail juvenile competition.

Harnish, Ryan A.↗

DOE OSTI2023

Weak Gravitational Lensing of Low Surface Brightness Galaxies in the DES Year 3 Catalog

We present galaxy-galaxy lensing measurements of a sample of low surface brightness galaxies (LSBGs) drawn from the Dark Energy Survey Year 3 (Y3) data. LSBGs are diffuse galaxies with a surface brightness dimmer than the ambient night sky. Given their faintness, the use of standard observational techniques proves challenging. Weak gravitational lensing probes both the baryonic and dark matter content of galaxies, rendering it a powerful technique to estimate LSBG masses. The LSBG lens sample consists of 23, 790 total extended galaxies separated into red and blue color types at $g-i\ge 0.60$ and $g-i\le 0.60$, respectively. We use the Y3 \metacal\ shape catalog as the source sample, with a number density of {\color{red}$5.59 \mathrm{gal}/\mathrm{arcmin}^2$}. We measure the tangential shear around the lens galaxies across angular scales of $0.25-400$ arcmin and find a signal-to-noise of 6.67 for red galaxies, 2.17 for blue galaxies, and 5.30 for the total sample. W e fit a model built from two NFW profiles corresponding to the LSBG dark matter subhalo and host halo to the red LSBG shear measurements with an MCMC. We estimate the host halo mass at $7.3 ^{+2.0}_{-1.6}\times 10^{12} M_\mathrm{\odot}$. We place a 95\% upper bound on the subhalo mass at $2.8\times 10^{11} M_\mathrm{\odot}$. We utilize the lens sample photometry to obtain an estimate of the red LSBG stellar mass distribution. We compare the ratio between the stellar mass and the subhalo mass to the parameterized, satellite-specific SHMR \citep{Moster2010}. This work represents the first example of an attempted constraint on the masses of LSBGs using weak gravitational lensing.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2021

Integrating Solar Energy, Desalination, and Electrolysis

Solar electricity enables the advancement and deployment of technologies that are strongly influenced by clean energy availability and cost. The economics of both desalination and hydrogen production from water electrolysis are dominated by the cost of energy, and the availability of inexpensive solar energy creates markets and offers incentives to the desalination and electrolyzer industries. In this report the production of high-purity water and hydrogen from seawater is focused on. Current electrolyzers require deionized water so they need to be coupled with desalination units. It is shown that such coupling is cost effective in hydrogen generation, and it also offers benefits to thermal desalination, which can utilize waste heat from electrolysis. Furthermore, such coupling can be optimized when electrolyzers operate at high current density, using low-cost solar and/or wind electricity, as such operation increases both hydrogen production and heat generation. Results of technoeconomic modeling of polymer electrolyte membrane electrolyzers define thresholds of electricity pricing, current density, and operating temperature that make clean electrolytic hydrogen cost competitive with hydrogen from steam methane reforming (SMR). By using 2020 hourly electricity pricing in California and Texas, it is estimated that hydrogen can be produced from seawater in coupled desalination-electrolyzer systems at prices near $2 kg -1 H 2 , reaching cost parity with hydrogen produced from SMR.

14 SOLAR ENERGY↗

DOE OSTI2020

Empirical correlations for prediction of minimum miscible pressure and near-miscible pressure interval for oil and CO 2 systems

Although near-miscible CO 2 flooding has recently received considerable attention, no criteria are available to predict its applicability to a specific reservoir. Evaluating the viability of near-miscible flooding requires experimental exploration of a specific region in pressure–temperature space. The near-miscible pressure field is bounded on one side in P, T space by the MMP (minimum miscible pressure). This paper provides robust empirical correlations to estimate the MMP for both pure and impure CO 2 and for prediction of the near-miscible pressure region for CO 2 -oil. Many slim tube analyses, lacking high density data points, systematically underestimate the MMP, when the near miscible region is not accounted for. They are based on 147 published data sets that include: slim tube experimental determination of MMP; interfacial tension (IFT) between oil and CO 2 ; concentration of solution gas; and purity of the CO 2 . This paper is the first to begin a systematic exploration of the pressure-temperature space within which near-miscible effects characterize CO 2 floods. Our new correlations provide a basis for identifying and investigating the nature of near miscible effects associated with existing CO 2 floods. For a case study of an offshore field we determined that lower and upper pressure boundaries for effective near-miscible flooding, are 0.87 MMP and 1.07 MMP at reservoir temperatures. The proposed model is the first empirical correlation for the prediction of near-miscible pressure region, it will provide the basis for both screening the relative potential of oil reservoirs for economically viable miscible or near-miscible CO 2 -flooding.

42 ENGINEERING↗

DOE OSTI2020

Conceptual Design and Rationale for a New Agrivoltaics Concept: Pastured-Raised Rabbits and Solar Farming

Land-use conflicts created by the growth of solar photovoltaics (PV) can be mitigated by applying the concept of agrivoltaics, that is, the co-development of land for both PV and agricultural purposes, to commercial-scale solar installations. In this study, we present a conceptual design for a novel agrivoltaic system based on pasture-fed rabbit farming and provide the technical, environmental and economic analyses to demonstrate the viability of the concept. Included in our analysis are the economic advantages to the PV operator of grazing rabbits at a density sufficient to control vegetative growth, thus reducing the economic and environmental costs of mowing; the dual-revenue stream from the sale of both rabbits and electricity, contrasted with estimates of the capital-investment costs for rabbits co-located with, and also independent of, PV; and the economic value to the rabbit farmer of higher colony-growth rates (made possible by the shading and predator protection provided by the PV arrays and of reduced fencing costs, which are the largest capital cost, by being able to leverage the PV systems for rabbit fencing. We also provide an environmental analysis that suggests that rabbit-PV farming is a pathway to a measurable reduction in agriculturally-generated greenhouse-gas emissions. Here, our calculations indicate that the co-location of solar and rabbit farms is a viable form of agrivoltaics, increasing overall site revenue by 2.5%-24.0% above projected electricity revenue depending on location and rental/ownership of rabbits, while providing a high-value agricultural product that, on a per weight basis, has significantly less environmental impact than cattle.

14 SOLAR ENERGY↗

DOE OSTI2025

Approach to Evaluating Reorganization Energies of Interfacial Electrochemical Reactions

Reaction rate coefficients for electron-transfer processes at the electrode–electrolyte interface are commonly estimated by using the Butler–Volmer equation, but their values are inaccurate beyond a few tenths of volts of overpotential. The Marcus–Hush–Chidsey (MHC) formalism yields correct asymptotic behavior of the rate coefficients vs applied overpotential but has complex dependencies on the redox system’s intrinsic parameters, which can be difficult to model or measure. In this work, we bridge the two kinetics formalisms to estimate the reorganization energy, one of the important parameters for the MHC formalism, and investigate its dependence on other intrinsic parameters such as activation barriers, electronic coupling strength, and the density of states of the electrode surface. We examine the sensitivity of the reorganization energy to these parameters, establish some general relationships for accurately predicting rate coefficients using the MHC formalism over a wide range of applied overpotentials, and compare this approach to calculating MHC rate constants with other empirical approaches for the mechanisms of CO 2 reduction on different metal electrode surfaces.

Butler−Volmer↗

DOE OSTI2020

Visualizing Orbital Content of Electronic Bands in Anisotropic 2D Semiconducting ReSe 2

Many properties of layered materials change as they are thinned from their bulk forms down to single layers, with examples including indirect-to-direct band gap transition in 2H semiconducting transition metal dichalcogenides as well as thickness-dependent changes in the valence band structure in post-transition-metal monochalcogenides and black phosphorus. Here, we use angle-resolved photoemission spectroscopy to study the electronic band structure of monolayer ReSe 2 , a semiconductor with a distorted 1T structure and in-plane anisotropy. By changing the polarization of incoming photons, we demonstrate that for ReSe 2 , in contrast to the 2H materials, the out-of-plane transition metal dz2 and chalcogen pz orbitals do not contribute significantly to the top of the valence band, which explains the reported weak changes in the electronic structure of this compound as a function of layer number. We estimate a band gap of 1.7 eV in pristine ReSe 2 using scanning tunneling spectroscopy and explore the implications on the gap following surface doping with potassium. Additionally, a lower bound of 1.4 eV is estimated for the gap in the fully doped case, suggesting that doping-dependent many-body effects significantly affect the electronic properties of ReSe 2 . Our results, supported by density functional theory calculations, provide insight into the mechanisms behind polarization-dependent optical properties of rhenium dichalcogenides and highlight their place among two-dimensional crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Ultraviolet spectroscopy of pressurized and supercritical carbon dioxide

Abstract Carbon dioxide (CO 2 ) is prevalent in planetary atmospheres and sees use in a variety of industrial applications. Despite its ubiquitous nature, its photochemistry remains poorly understood. In this work we explore the density dependence of pressurized and supercritical CO 2 electronic absorption spectra by vacuum ultraviolet spectroscopy over the wavelength range 1455-2000 Å. We show that the lowest absorption band transition energy is unaffected by a density increase up to and beyond the thermodynamic critical point (137 bar, 308 K). However, the diffuse vibrational structure inherent to the spectrum gradually decreases in magnitude. This effect cannot be explained solely by collisional broadening and/or dimerization. We suggest that at high densities close proximity of neighboring CO 2 molecules with a variety of orientations perturbs the multiple monomer electronic state potential energy surfaces, facilitating coupling between binding and dissociative states. We estimate a critical radius of ~4.1 Å necessary to cause such perturbations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Testing general relativity on cosmological scales at redshift z ∼ 1.5 with quasar and CMB lensing

ABSTRACT We test general relativity (GR) at the effective redshift $\bar{z} \sim 1.5$ by estimating the statistic EG, a probe of gravity, on cosmological scales $19 - 190\, h^{-1}{\rm Mpc}$. This is the highest redshift and largest scale estimation of EG so far. We use the quasar sample with redshifts 0.8 < z < 2.2 from Sloan Digital Sky Survey IV extended Baryon Oscillation Spectroscopic Survey Data Release 16 as the large-scale structure (LSS) tracer, for which the angular power spectrum $C_\ell ^{qq}$ and the redshift-space distortion parameter β are estimated. By cross-correlating with the Planck 2018 cosmic microwave background (CMB) lensing map, we detect the angular cross-power spectrum $C_\ell ^{\kappa q}$ signal at $12\, \sigma$ significance. Both jackknife resampling and simulations are used to estimate the covariance matrix (CM) of EG at five bins covering different scales, with the later preferred for its better constraints on the covariances. We find EG estimates agree with the GR prediction at $1\, \sigma$ level over all these scales. With the CM estimated with 300 simulations, we report a best-fitting scale-averaged estimate of $E_G(\bar{z})=0.30\pm 0.05$, which is in line with the GR prediction $E_G^{\rm GR}(\bar{z})=0.33$ with Planck 2018 CMB + BAO matter density fraction Ωm = 0.31. The statistical errors of EG with future LSS surveys at similar redshifts will be reduced by an order of magnitude, which makes it possible to constrain modified gravity models.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2026

Deep-field analytical calibration

The next generation of imaging surveys, including the Vera C. Rubin Observatory Legacy Survey of Space and Time (LSST), Euclid, and the Nancy Grace Roman Space Telescope, will provide unprecedented constraints on cosmology using weak gravitational lensing. To fully exploit this statistical power, shear measurement methods must achieve sub- per cent accuracy while mitigating systematic biases from noise, the point-spread function (PSF), blending, and shear-dependent detection. The analytical calibration framework (AnaCal) has demonstrated such accuracy but requires adding noise to images, reducing effective depth. We introduce Deep-Field Analytical Calibration (DEEP-FIELD AnaCal), an extension of AnaCal that uses deep-field images to compute shear responses while preserving the statistical power of wide-field data. We validate DEEP-FIELD AnaCal on isolated and blended galaxy image simulations with LSST-like conditions, finding it meets the stringent requirement of multiplicative bias $|m| < 3\times 10^{-3}$ at 99.7 per cent confidence. Compared to standard AnaCal applied to wide-field images, DEEP-FIELD AnaCal increases the effective galaxy number density from 17 to 30 arcmin$^{-2}$ for simulated 10-yr LSST data. With deep fields $10\times$ longer than the wide field, we find pixel noise variance in shear estimation is reduced by 30 per cent and overall uncertainty by $\sim 25~{{\ \rm per\ cent}}$. Finally, using the LSST Deep Drilling Fields strategy, we assess sample variance and find an equivalent calibration uncertainty of $\lesssim 0.3~{{\ \rm per\ cent}}$. These results demonstrate that DEEP-FIELD AnaCal offers a promising path to achieve the required shear calibration for upcoming weak lensing surveys.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2024

Multimodal fission from self-consistent calculations

When multiple fission modes coexist in a given nucleus, distinct fragment yield distributions appear. Multimodal fission has been observed in a number of fissioning nuclei spanning the nuclear chart, and this phenomenon is expected to affect the nuclear abundances synthesized during the rapid neutron-capture process (𝑟-process). In this study, we generalize the previously proposed hybrid model for fission-fragment yield distributions to predict competing fission modes and estimate the resulting yield distributions. Here, our framework allows for a comprehensive large-scale calculation of fission-fragment yields suited for 𝑟-process nuclear network studies. Nuclear density functional theory is employed to obtain the potential energy and collective inertia tensor on a multidimensional collective space defined by mass multipole moments. Fission pathways and their relative probabilities are determined using the nudged elastic band method. Based on this information, mass and charge fission yields are predicted using the recently developed hybrid model. Fission properties of fermium isotopes are calculated in the axial quadrupole-octupole collective space for three energy density functionals (EDFs). Disagreement between the EDFs appears when multiple fission modes are present. Within our framework, the UNEDF⁢1 HFB EDF agrees best with experimental data. Calculations in the axial quadrupole-octupole-hexadecapole collective space improve the agreement with the experiment for SkM*. We also discuss the sensitivity of fission predictions on the choice of EDF for several superheavy nuclei. Fission-fragment yield predictions for nuclei with multiple fission modes are sensitive to the underlying EDF. For large-scale calculations in which a minimal number of collective coordinates is considered, UNEDF⁢1 HFB provides the best description of experimental data, though the sensitivity motivates robust quantification of the uncertainties of the theoretical model.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2024

Reliability comparisons between additively manufactured and conventional SiC–Si ceramic composites

Abstract An additively manufactured reaction‐bonded silicon carbide ceramic composite is fabricated using a bimodal powder feedstock and the binder‐jetting printing technique. On fabricating, the ceramic is investigated to report its composition, mechanical, and thermal properties at room temperature and high temperatures (up to 750). The ceramic has a density of 2.76 g/cc, and shows a hardness of 21.74 GPa, and a flexure strength of 207.5 MPa at room temperature. The mechanical property of flexure strength is used to estimate its failure probability under applied stress, using a Weibull distribution. The mechanical properties and failure probabilities are compared with those of conventionally fabricated reaction‐bonded silicon carbide ceramics reported in the literature. These ceramics were fabricated using methods such as slip‐casting, compacting, and tape‐casting. The comparison is used to elucidate the advantages and areas of improvement of the present additive manufacturing technique for reaction‐bonded ceramics.

14 SOLAR ENERGY↗

DOE OSTI2026

Galaxy Clusters Selected via the Sunyaev-Zel'dovich Effect in 5 year data from the SPT-3G Main Survey

We report a new galaxy cluster catalog, selected using the thermal Sunyaev-Zel'dovich (SZ) effect, from 5 years of observations of the SPT-3G Main field. Drawn from arcminute-resolution data with white noise levels of 3.2, 2.5, and 8.9 $μ$K-arcmin at 95, 150, and 220 GHz, respectively, the sample consists of 8,892 cluster candidates detected above significance $ξ=4$, with an expected purity of $>82\%$ (4,480 at $ξ\ge5$ with purity $>99\%$). Using optical and infrared data we have confirmed 7,190 candidates as clusters. The sample spans a mass range $7.9 \times 10^{13}M_\odot/h_{70}< M_\textrm{500c} < 1.6 \times 10^{15}M_\odot/h_{70}$ with a median mass of $1.65 \times 10^{14}M_\odot/h_{70}$, and a redshift range of $0.0371$ and 271 at $z>1.5$. Compared to previous SZ cluster samples from South Pole Telescope and Atacama Cosmology Telescope data, the SPT-3G sample is highly consistent in mass and redshift but is significantly deeper, with per-cluster detection signal-to-noise 2-4 times higher and a cluster density of 4.5 confirmed clusters/deg$^2$. We cross match with eRASS1 cluster and point source catalogs, finding 1,279 and 1,319 matches, respectively. The SPT and eROSITA cluster mass estimates are in relatively good agreement. We perform a series of validation checks using both internal data splits and comparisons to external samples. These tests show increasing correlated (dusty) emission with redshift, with a $\sim17\times$ larger 220 GHz temperature increment for clusters at $z\sim1.5$ than $z\sim0.25$, but only weak evidence for correlated synchrotron emission. Finally, a number of clusters are flagged as candidate strong gravitational lenses.

Bleem, L. E. [Argonne (main); Chicago U., KICP; Ch↗

DOE OSTI2022

Updated Godiva-IV Benchmark Preview

A note of errata prepended to the Godiva-IV delayed-critical benchmark (HEU-MET-FAST- 086) identifies two corrections to be made to the model: The glory hole in the spindle should be made larger, and the height of the safety block should be made smaller (and therefore its density made larger). In addition, the safety block at its full-in position is closer to the inner subassembly plate than was modeled in the benchmark. These changes have been made to HEU-MET-FAST-086 Case 4 in order to estimate the effect on $\kappa$ eff and on the neutron flux spectrum. Using smaller separation, a smaller safety block, and a larger glory hole caused keff to increase by 453 ± 1 pcm from the benchmark. The latest nuclear data, ENDF/B-VIII.0, have also been used, causing $\kappa$ eff to increase another 37 ± 1 pcm. Flux spectra were compared in a modeled fission foil (near the center of Godiva-IV in the glory hole) and at three external (point) detectors. Within the fission foil, using ENDF/B-VIII.0 induced changes in the flux spectrum similar in size to the changes due to using smaller separation, a smaller safety block, and a larger glory hole. At the detectors, using ENDF/B- VIII.0 induced changes in the flux spectrum much larger than those due to changing the model. In other words, the corrections to the benchmark model cause a large increase in $\kappa$ eff , but the changes to the neutron flux spectrum are small compared to those caused by using the latest nuclear data. This study presents a preview of results expected during the reevaluation of the Godiva IV benchmark, but it is not a substitute for the full reevaluation.A note of errata prepended to the Godiva-IV delayed-critical benchmark (HEU-MET-FAST- 086) identifies two corrections to be made to the model: The glory hole in the spindle should be made larger, and the height of the safety block should be made smaller (and therefore its density made larger). In addition, the safety block at its full-in position is closer to the inner subassembly plate than was modeled in the benchmark. These changes have been made to HEU-MET-FAST-086 Case 4 in order to estimate the effect on $\kappa$ eff and on the neutron flux spectrum. Using smaller separation, a smaller safety block, and a larger glory hole caused $\kappa$ eff to increase by 453 ± 1 pcm from the benchmark. The latest nuclear data, ENDF/B-VIII.0, have also been used, causing $\kappa$ eff to increase another 37 ± 1 pcm. Flux spectra were compared in a modeled fission foil (near the center of Godiva-IV in the glory hole) and at three external (point) detectors. Within the fission foil, using ENDF/B-VIII.0 induced changes in the flux spectrum similar in size to the changes due to using smaller separation, a smaller safety block, and a larger glory hole. At the detectors, using ENDF/B- VIII.0 induced changes in the flux spectrum much larger than those due to changing the model. In other words, the corrections to the benchmark model cause a large increase in $\kappa$ eff , but the changes to the neutron flux spectrum are small compared to those caused by using the latest nuclear data. This study presents a preview of results expected during the reevaluation of the Godiva IV benchmark, but it is not a substitute for the full reevaluation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2023

Theoretical Insights on the Fragmentation of Cellulosic Oligomers to Form Hydroxyacetone and Hydroxyacetaldehyde

The presence of heavy unknown oligomeric sugar products in bio-oil is evidenced in experimental results reported in the literature. In this paper, we study the fragmentation reactions yielding acetol and glycolaldehyde from oligomeric sugars following previous work on dehydration reactions to propose structures of these oligomers. Acetol and glycolaldehyde are primary products of cellulose fast pyrolysis but the fragmentation reaction mechanism of these compounds from oligomers merits further study. The density functional theory (DFT) approach was employed to study this reaction. Results revealed that acetol and glycolaldehyde fragments are favorably removed from the non-reducing end based on their thermodynamic stabilities. Theoretical FTIR and NMR spectra were calculated to aid in understanding the structures of the oligomeric sugars. Also, the thermodynamics and physical properties of these compounds were estimated using the Group Contribution Method (GCM). In conclusion, these properties are essential in the design of processing technologies and the upgrading of products.

10 SYNTHETIC FUELS↗

DOE OSTI2023

High-throughput ab initio reaction mechanism exploration in the cloud with automated multi-reference validation

Quantum chemical calculations on atomistic systems have evolved into a standard approach to studying molecular matter. These calculations often involve a significant amount of manual input and expertise, although most of this effort could be automated, which would alleviate the need for expertise in software and hardware accessibility. Here, we present the AutoRXN workflow, an automated workflow for exploratory high-throughput electronic structure calculations of molecular systems, in which (i) density functional theory methods are exploited to deliver minimum and transition-state structures and corresponding energies and properties, (ii) coupled cluster calculations are then launched for optimized structures to provide more accurate energy and property estimates, and (iii) multi-reference diagnostics are evaluated to back check the coupled cluster results and subject them to automated multi-configurational calculations for potential multi-configurational cases. All calculations are carried out in a cloud environment and support massive computational campaigns. Key features of all components of the AutoRXN workflow are autonomy, stability, and minimum operator interference. We highlight the AutoRXN workflow with the example of an autonomous reaction mechanism exploration of the mode of action of a homogeneous catalyst for the asymmetric reduction of ketones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗