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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.

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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
NASA NTRS1973

Editing ERTS-1 data to exclude land aids cluster analysis of water targets

The author has identified the following significant results. It has been determined that an increase in the number of spectrally distinct coastal water types is achieved when data values over the adjacent land areas are excluded from the processing routine. This finding resulted from an automatic clustering analysis of ERTS-1 system corrected MSS scene 1002-18134 of 25 July 1972 over Monterey Bay, California. When the entire study area data set was submitted to the clustering only two distinct water classes were extracted. However, when the land area data points were removed from the data set and resubmitted to the clustering routine, four distinct groupings of water features were identified. Additionally, unlike the previous separation, the four types could be correlated to features observable in the associated ERTS-1 imagery. This exercise demonstrates that by proper selection of data submitted to the processing routine, based upon the specific application of study, additional information may be extracted from the ERTS-1 MSS data.

Erb, R. B.↗
DOE OSTI2023

Dark Energy Survey Year 3 results: magnification modelling and impact on cosmological constraints from galaxy clustering and galaxy–galaxy lensing

We study the effect of magnification in the Dark Energy Survey Year 3 analysis of galaxy clustering and galaxy–galaxy lensing, using two different lens samples: a sample of luminous red galaxies, redMaGiC, and a sample with a redshift-dependent magnitude limit, MagLim. We account for the effect of magnification on both the flux and size selection of galaxies, accounting for systematic effects using the Balrog image simulations. We estimate the impact of magnification on the galaxy clustering and galaxy–galaxy lensing cosmology analysis, finding it to be a significant systematic for the MagLim sample. We show cosmological constraints from the galaxy clustering autocorrelation and galaxy–galaxy lensing signal with different magnifications priors, finding broad consistency in cosmological parameters in ΛCDM and wCDM. However, when magnification bias amplitude is allowed to be free, we find the two-point correlation functions prefer a different amplitude to the fiducial input derived from the image simulations. We validate the magnification analysis by comparing the cross-clustering between lens bins with the prediction from the baseline analysis, which uses only the autocorrelation of the lens bins, indicating that systematics other than magnification may be the cause of the discrepancy. We show that adding the cross-clustering between lens redshift bins to the fit significantly improves the constraints on lens magnification parameters and allows uninformative priors to be used on magnification coefficients, without any loss of constraining power or prior volume concerns.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Main-sequence Scatter is Real: The Joint Dependence of Galaxy Clustering on Star Formation and Stellar Mass

We present new measurements of the clustering of stellar-mass-complete samples of ∼40,000 SDSS galaxies at z ∼ 0.03 as a joint function of stellar mass and specific star formation rate (sSFR). Our results confirm what Coil et al. find at z ∼ 0.7: galaxy clustering is a stronger function of sSFR at fixed stellar mass than of stellar mass at fixed sSFR. We also find that galaxies above the star-forming main sequence (SFMS) with higher sSFR are less clustered than galaxies below the SFMS with lower sSFR, at a given stellar mass. A similar trend is present for quiescent galaxies. This confirms that main-sequence scatter, and scatter within the quiescent sequence, is physically connected to the large-scale cosmic density field. We compare the resulting galaxy bias versus sSFR, and relative bias versus sSFR ratio, for different galaxy samples across 0 < z < 1.2 to mock galaxy catalogs based on the empirical galaxy evolution model of Behroozi et al. This model fits PRIMUS and DEEP2 clustering data well at intermediate redshift, but agreement with SDSS is not as strong. We show that increasing the correlation between galaxy SFR and halo accretion rate at z ∼ 0 in the model substantially improves agreement with SDSS data. Mock catalogs suggest that central galaxies contribute substantially to the dependence of clustering on sSFR at a given stellar mass and that the signal is not simply an effect of satellite galaxy fraction differences with sSFR. Our results are highly constraining for galaxy evolution models and show that the stellar-to-halo mass relation depends on sSFR.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS2012

The Atacama Cosmology Telescope: Relation Between Galaxy Cluster Optical Richness and Sunyaev-Zel'dovich Effect

We present the measured Sunyaev-Zel'dovich (SZ) flux from 474 optically-selected MaxBCG clusters that fall within the Atacama Cosmology Telescope (ACT) Equatorial survey region. The ACT Equatorial region used in this analysis covers 510 square degrees and overlaps Stripe 82 of the Sloan Digital Sky Survey. We also present the measured SZ flux stacked on 52 X-ray-selected MCXC clusters that fall within the ACT Equatorial region and an ACT Southern survey region covering 455 square degrees. We find that the measured SZ flux from the X-ray-selected clusters is consistent with expectations. However, we find that the measured SZ flux from the optically-selected clusters is both significantly lower than expectations and lower than the recovered SZ flux measured by the Planck satellite. Since we find a lower recovered SZ signal than Planck, we investigate the possibility that there is a significant offset between the optically-selected brightest cluster galaxies (BCGs) and the SZ centers, to which ACT is more sensitive due to its finer resolution. Such offsets can arise due to either an intrinsic physical separation between the BCG and the center of the gas concentration or from misidentification of the cluster BCG. We find that the entire discrepancy for both ACT and Planck can be explained by assuming that the BCGs are offset from the SZ maxima with a uniform random distribution between 0 and 1.5 Mpc. In contrast, the physical separation between BCGs and X-ray peaks for an X-ray-selected subsample of MaxBCG clusters shows a much narrower distribution that peaks within 0.2 Mpc. We conclude that while offsets between BCGs and SZ peaks may be an important component in explaining the discrepancy, it is likely that a combination of factors is responsible for the ACT and Planck measurements. Several effects that can lower the SZ signal equally for both ACT and Planck, but not explain the difference in measured signals, include a larger percentage of false detections in the MaxBCG sample, a lower normalization of the mass-richness relation, radio or infrared galaxy contamination of the SZ flux, and a low intrinsic SZ signal. In the latter two cases, the effects would need to be preferentially more significant in the optically-selected MaxBCG sample than in the MCXC X-ray sample.

Sehgal, Neelima↗
NASA NTRS2020

Clouds and Convective Self-Aggregation in a Multi-Model Ensemble of Radiative-Convective Equilibrium Simulations

The Radiative-Convective Equilibrium Model Intercomparison Project (RCEMIP) is an intercomparison of multiple types of numerical models configured in radiative-convective56equilibrium (RCE). RCE is an idealization of the tropical atmosphere that has long been used to study basic questions in climate science. Here, we employ RCE to investigate the role that clouds and convective activity play in determining cloud feedbacks, climatecsensitivity, the state of convective aggregation, and the equilibrium climate. RCEMIP is unique amongst intercomparisons in its inclusion of a wide range of model types, including atmospheric general circulation models (GCMs), single column models (SCMs), cloud-resolving models (CRMs), large eddy simulations (LES), and global cloud-resolving models (GCRMs). The first results are presented from the RCEMIP ensemble of more than 30 models. While there are large differences across the RCEMIP ensemble in the representation of mean profiles of temperature, humidity, and cloudiness, in a majority of models anvil clouds rise, warm, and decrease in area coverage in response to an increase in sea surface temperature (SST). Nearly all models exhibit self-aggregation in large domains and agree that self-aggregation acts to dry and warm the troposphere, reduce high cloudiness, and increase cooling to space. The degree of self-aggregation exhibits no clear tendency with warming. There is a wide range of climate sensitivities, but models with parameterized convection tend to have lower climate sensitivities than models with explicit convection. In models with parameterized convection, aggregated simulations have lower climate sensitivities than un-aggregated simulations. Plain Language Summary This study investigates tropical clouds and climate using results from more than 30 different numerical models set up in a simplified framework. The dataset of model simulations is unique in that it includes a wide range of model types configured in a consistent manner. We address some of the biggest open questions in climate science, including how cloud properties change with warming and the role that the tendency of clouds to form clusters plays in determining the average climate and how climate changes. While there are large differences in how the different models simulate average temperature, humidity, and cloudiness, in a majority of models, the amount of high clouds decreases as climate warms. Nearly all models simulate a tendency for clouds to cluster together. There is agreement that when the clouds are clustered, the atmosphere is drier with fewer clouds overall. We don’t find a conclusive result for how cloud clustering changes as the climate warms.

Allison A. Wing↗
DOE OSTI2022

ezAlign

The ezAlign is aimed at clustering coarse grain simulation to find common or uncommon occurrences and convert coarse (CG) grained coordinate and topology files to atomistic formats. We use a PointNet based approach to map individual frames of simulation to points in a latent space. These points are then clustered using a variety of clustering methods. Clusters are analyzed to associate them with states in the simulation. Frames can be chosen from these clusters based on proximity to cluster centers. ezAlign takes CG coordinate and topology files and converts and outputs their corresponding atomistic formats using an alignment and relaxation procedure. ezAlign is designed to convert complex, solvated biological systems including lipid membranes with drug-like molecules using GROMACS. A GROMACS checkpoint (.cpt) file is also outputted to enable continuation simulations that retain the equilibrated atomic velocities. Independent atomistic coordinates and topologies for every molecule must already be included in ezAlign/files. A number of commonly simulated biological molecules are currently provided.

Bennett, WilliamF.↗
DOE OSTI2021

A multi-step nucleation process determines the kinetics of prion-like domain phase separation

Compartmentalization by liquid-liquid phase separation (LLPS) has emerged as a ubiquitous mechanism underlying the organization of biomolecules in space and time. Here, we combine rapid-mixing time-resolved small-angle X-ray scattering (SAXS) approaches to characterize the assembly kinetics of a prototypical prion-like domain with equilibrium techniques that characterize its phase boundaries and the size distribution of clusters prior to phase separation. We find two kinetic regimes on the micro- to millisecond timescale that are distinguished by the size distribution of clusters. At the nanoscale, small complexes are formed with low affinity. After initial unfavorable complex assembly, additional monomers are added with higher affinity. At the mesoscale, assembly resembles classical homogeneous nucleation. Careful multi-pronged characterization is required for the understanding of condensate assembly mechanisms and will promote understanding of how the kinetics of biological phase separation is encoded in biomolecules.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Coupled-cluster theory for strong entanglement in nuclei

Atomic nuclei can exhibit shape coexistence and multireference physics that enters in their ground states, and accurately capturing the ensuing correlations and entanglement is challenging. Here, we address this problem by applying single-reference coupled-cluster theory based on spherical and deformed reference states and the tailored coupled-cluster method. The latter combines configuration interactions to capture static correlations with coupled-cluster theory for dynamic correlations. We compute the atomic nuclei 12 C, 28 Si, and 56 Ni and find that the tailored coupled-cluster method and the single-reference approach based on a deformed Hartree-Fock state yield the most accurate results.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1993

A catalog of intracluster gas temperatures

We have searched the Einstein Monitor Proportional Counter (MPC) data base for observations of clusters of galaxies. By coadding the MPC spectra obtained during all pointed observations of clusters with IPC count rates greater than 0.1 counts/s, we have obtained sufficient photon statistics to estimate the X-ray temperature of 84 clusters. Combining the MPC results with EXOSAT and Ginga results reported in the literature yields a combined sample of 104 clusters with known X-ray temperatures. One of the best studied X-ray correlations between clusters is that between their X-ray luminosity and gas temperature. We show that the best-fit power-law relation for our combined cluster sample can be explained by the observed increase in the gas-to-stellar mass ratio between low- and high-temperature clusters. The statistical significance of any evolution in our combined X-ray sample has been examined and compared with the statistical properties of clusters culled from optical catalogs. We find that there is strong evidence for a decrease in the X-ray luminosity of optically rich clusters beyond z approximately about 0.06. This result is used to estimate the normalization of the primordial power spectrum of density fluctuations.

David, L. P.↗
NASA NTRS2012

The Resolved Stellar Population in 50 Regions of M83 from HST/WFC3 Early Release Science Observations

We present a multi-wavelength photometric study of approximately 15,000 resolved stars in the nearby spiral galaxy M83 (NGC 5236, D = 4.61 Mpc) based on Hubble Space Telescope Wide Field Camera 3 observations using four filters: F336W, F438W, F555W, and F814W. We select 50 regions (an average size of 260 pc by 280 pc) in the spiral arm and inter-arm areas of M83 and determine the age distribution of the luminous stellar populations in each region. This is accomplished by correcting for extinction toward each individual star by comparing its colors with predictions from stellar isochrones.We compare the resulting luminosity-weighted mean ages of the luminous stars in the 50 regions with those determined from several independent methods, including the number ratio of red-to-blue supergiants, morphological appearance of the regions, surface brightness fluctuations, and the ages of clusters in the regions. We find reasonably good agreement between these methods. We also find that young stars are much more likely to be found in concentrated aggregates along spiral arms, while older stars are more dispersed. These results are consistent with the scenario that star formation is associated with the spiral arms, and stars form primarily in star clusters and then disperse on short timescales to form the field population. The locations ofWolf-Rayet stars are found to correlate with the positions of many of the youngest regions, providing additional support for our ability to accurately estimate ages. We address the effects of spatial resolution on the measured colors, magnitudes, and age estimates. While individual stars can occasionally show measurable differences in the colors and magnitudes, the age estimates for entire regions are only slightly affected.

Hubble Space Telescope↗
NASA NTRS1994

Hot gas in the cold dark matter scenario: X-ray clusters from a high-resolution numerical simulation

A new, three-dimensional, shock-capturing hydrodynamic code is utilized to determine the distribution of hot gas in a standard cold dark matter (CDM) model of the universe. Periodic boundary conditions are assumed: a box with size 85 h(exp -1) Mpc having cell size 0.31 h(exp -1) Mpc is followed in a simulation with 270(exp 3) = 10(exp 7.3) cells. Adopting standard parameters determined from COBE and light-element nucleosynthesis, sigma(sub 8) = 1.05, omega(sub b) = 0.06, and assuming h = 0.5, we find the X-ray-emitting clusters and compute the luminosity function at several wavelengths, the temperature distribution, and estimated sizes, as well as the evolution of these quantities with redshift. We find that most of the total X-ray emissivity in our box originates in a relatively small number of identifiable clusters which occupy approximately 10(exp -3) of the box volume. This standard CDM model, normalized to COBE, produces approximately 5 times too much emission from clusters having L(sub x) is greater than 10(exp 43) ergs/s, a not-unexpected result. If all other parameters were unchanged, we would expect adequate agreement for sigma(sub 8) = 0.6. This provides a new and independent argument for lower small-scale power than standard CDM at the 8 h(exp -1) Mpc scale. The background radiation field at 1 keV due to clusters in this model is approximately one-third of the observed background, which, after correction for numerical effects, again indicates approximately 5 times too much emission and the appropriateness of sigma(sub 8) = 0.6. If we have used the observed ratio of gas to total mass in clusters, rather than basing the mean density on light-element nucleosynthesis, then the computed luminosity of each cluster would have increased still further, by a factor of approximately 10. The number density of clusters increases to z approximately 1, but the luminosity per typical cluster decreases, with the result that evolution in the number density of bright clusters is moderate in this redshift range, showing a broad peak near z = 0.7, and then a rapid decline above redshift z = 3. Detailed computations of the luminosity functions in the range L(sub x) = 10(exp 40) - 10(exp 44) ergs/s in various energy bands are presented for both cluster central regions and total luminosities to be used in comparison with ROSAT and other observational data sets. The quantitative results found disagree significantly with those found by other investigators using semianalytic techniques. We find little dependence of core radius on cluster luminosity and a dependence of temperature on luminosity given by log kT(sub x) = A + B log L(sub x), which is slightly steeper (B = 0.38) than is indicated by observations. Computed temperatures are somewhat higher than observed, as expected, in that COBE-normalized CDM has too much power on the relevant scales. A modest average temperature gradient is found, with temperatures dropping to 90% of central values at 0.4 h(exp -1) Mpc and 70% of central values at 0.9 h(exp -1) Mpc. Examining the ratio of gas to total mass in the clusters normalized to Omega(sub B) h(exp 2) = 0.015, and comparing with observations, we conclude, in agreement with White (1991), that the cluster observations argue for an open universe.

Kang, Hyesung↗
DOE OSTI2026

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↗
DOE OSTI2022

The DESI N -body simulation project – I. Testing the robustness of simulations for the DESI dark time survey

ABSTRACT Analysis of large galaxy surveys requires confidence in the robustness of numerical simulation methods. The simulations are used to construct mock galaxy catalogues to validate data analysis pipelines and identify potential systematics. We compare three N-body simulation codes, abacus, gadget-2, and swift, to investigate the regimes in which their results agree. We run N-body simulations at three different mass resolutions, 6.25 × 108, 2.11 × 109, and 5.00 × 109 h−1 M⊙, matching phases to reduce the noise within the comparisons. We find systematic errors in the halo clustering between different codes are smaller than the Dark Energy Spectroscopic Instrument (DESI) statistical error for $s\ \gt\ 20\ h^{-1}$ Mpc in the correlation function in redshift space. Through the resolution comparison we find that simulations run with a mass resolution of 2.1 × 109 h−1 M⊙ are sufficiently converged for systematic effects in the halo clustering to be smaller than the DESI statistical error at scales larger than $20\ h^{-1}$ Mpc. These findings show that the simulations are robust for extracting cosmological information from large scales which is the key goal of the DESI survey. Comparing matter power spectra, we find the codes agree to within 1 per cent for k ≤ 10 h Mpc−1. We also run a comparison of three initial condition generation codes and find good agreement. In addition, we include a quasi-N-body code, FastPM, since we plan use it for certain DESI analyses. The impact of the halo definition and galaxy–halo relation will be presented in a follow-up study.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1992

Observation of the Coma cluster of galaxies with ROSAT during the all-sky survey

The Coma cluster of galaxies was observed with the position sensitive proportional counter (PSPC) during the ROSAT all sky survey. We find evidence for substructure in this cluster. Diffuse X-ray emission is detected from the regions of the NGC 4839 and 4911 subgroups at 6 percent and 1 percent of the total cluster emission respectively. There may be emission associated with the NGC 4874 and 4889 subgroups as well. The NGC 4839 group appears to be in the process of merging with the cluster. These X-ray data show that at least some of the groups previously found in projection are in fact physical objects possessing potential wells deep enough to trap their own X-ray gas. Because of the unlimited field of view of the all sky survey and the low background of the PSPC, we were able to measure the azimuthally averaged surface brightness of Coma out to approximately 100 arcmin, twice as far as was previously possible. Given the validity of our mass models, these new X-ray data imply that within 5/h(50) Mpc the binding mass of the Coma cluster is 1.8 +/- 0.6 x 10 exp 15/h(50) solar mass, and the fraction of cluster mass contained in hot gas is 0.30 +/- 0.14h(50) exp -3/2. Furthermore, the binding mass is more centrally concentrated than is the X-ray gas.

Briel, U. G.↗
NASA NTRS2001

Stellar Evolution in Starburst Galaxies

The main thrust of the program was to obtain UV spectroscopy of a number of massive and hot luminous (OB type) stars in the nearby galaxy called the Small Magellanic Cloud (SMC). The objective was to analyze their atmospheres and winds so as to determine the effect of the lower abundance of the SIVIC on these parameters. Furthermore, the differences in evolution could be investigated. Additionally, the UV spectra themselves would be suitably weighted and systematically combined to provide a template for comparison to very distant galaxies formed in the early history of the Universe which also have a low abundance of elements. The spectra have been obtained and the analysis is proceeding, primarily by the groups in Munich and at STScl who are the leads for this project. Given the important role of the nearby SMC galaxy as a template of low metal abundance, I have begun to investigate the YOUNGEST phases of massive star birth, before the most massive and hottest stars become optically visible. Typically these stars form in clusters, in some cases having tens to hundreds of OB type stars. In this phase, each star is still buried in its natal cloud and visible only in the infrared (IR) from its self-heated dust and/or from radio free-free emission of the surrounding hydrogen (HII) region. Efforts to find and identify these buried clusters were conducted using a large radio telescope. A number of these were found and further analysis of the data is underway. These clusters are not visible optically, but ought to be seen in the IR, and are a likely topic for HST photometry on NICMOS. A proposal to do this will be made next semester. These objects are the precursors of the optically visible clusters that contain massive and hot luminous stars.

Conti, Peter↗
NASA NTRS1979

On the clustering of multidimensional pictorial data

Obvious approaches to reducing the cost (in computer resources) of applying current clustering techniques to the problem of remote sensing are discussed. The use of spatial information in finding fields and in classifying mixture pixels is examined, and the AMOEBA clustering program is described. Internally, a pattern recognition program, from without, AMOEBA appears to be an unsupervised clustering program. It is fast and automatic. No choices (such as arbitrary thresholds to set split/combine sequences) need be made. The problem of finding the number of clusters is solved automatically. At the conclusion of the program, all points in the scene are classified; however, a provision is included for a reject classification of some points which, within the theoretical framework, cannot rationally be assigned to any cluster.

Bryant, J. D.↗
DOE OSTI2022

Shocks in the stacked Sunyaev-Zel’dovich profiles of clusters II: Measurements from SPT-SZ + Planck Compton- y map

ABSTRACT We search for the signature of cosmological shocks in stacked gas pressure profiles of galaxy clusters using data from the South Pole Telescope (SPT). Specifically, we stack the latest Compton-y maps from the 2500 deg2 SPT-SZ survey on the locations of clusters identified in that same data set. The sample contains 516 clusters with mean mass $\langle M_{\rm 200m}\rangle = 10^{14.9} \, {\rm M}_\odot$ and redshift 〈z〉 = 0.55. We analyse in parallel a set of zoom-in hydrodynamical simulations from the three hundred project. The SPT-SZ data show two features: (i) a pressure deficit at R/R200m = 1.08 ± 0.09, measured at 3.1σ significance and not observed in the simulations, and; (ii) a sharp decrease in pressure at R/R200m = 4.58 ± 1.24 at 2.0σ significance. The pressure deficit is qualitatively consistent with a shock-induced thermal non-equilibrium between electrons and ions, and the second feature is consistent with accretion shocks seen in previous studies. We split the cluster sample by redshift and mass, and find both features exist in all cases. There are also no significant differences in features along and across the cluster major axis, whose orientation roughly points towards filamentary structure. As a consistency test, we also analyse clusters from the Planck and Atacama Cosmology Telescope Polarimeter surveys and find quantitatively similar features in the pressure profiles. Finally, we compare the accretion shock radius ($R_{\rm sh,\, acc}$) with existing measurements of the splashback radius (Rsp) for SPT-SZ and constrain the lower limit of the ratio, $R_{\rm sh,\, acc}/R_{\rm sp}\gt 2.16 \pm 0.59$.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Improving gas adsorption modeling for MOFs by local calibration of Hubbard U parameters

While computational screening with density functional theory (DFT) is frequently employed for the screening of metal–organic frameworks (MOFs) for gas separation and storage, commonly applied generalized gradient approximations (GGAs) exhibit self-interaction errors, which hinder the predictions of adsorption energies. We investigate the Hubbard U parameter to augment DFT calculations for full periodic MOFs, targeting a more precise modeling of gas molecule–MOF interactions, specifically for N2, CO2, and O2. We introduce a calibration scheme for the U parameter, which is tailored for each MOF, by leveraging higher-level calculations on the secondary building unit (SBU) of the MOF. When applied to the full periodic MOF, the U parameter calibrated against hybrid HSE06 calculations of SBUs successfully reproduces hybrid-quality calculations of the adsorption energy of the periodic MOF. The mean absolute deviation of adsorption energies reduces from 0.13 eV for a standard GGA treatment to 0.06 eV with the calibrated U, demonstrating the utility of the calibration procedure when applied to the full MOF structure. Furthermore, attempting to use coupled cluster singles and doubles with perturbative triples calculations of isolated SBUs for this calibration procedure shows varying degrees of success in predicting the experimental heat of adsorption. It improves accuracy for N2 adsorption for cases of overbinding, whereas its impact on CO2 is minimal, and ambiguities in spin state assignment hinder consistent improvements of O2 adsorption. Our findings emphasize the limitations of cluster models and advocate the use of full periodic MOF systems with a calibrated U parameter, providing a more comprehensive understanding of gas adsorption in MOFs.

Chemistry↗