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DOE OSTI2022

Unveiling the mechanism of the photocatalytic reduction of CO 2 to formate promoted by porphyrinic Zr-based metal–organic frameworks

A complete picture of the reaction mechanism responsible for the photocatalytic reduction of CO 2 into formate promoted by the Zr-based porphyrinic MOF-545 (PCN-222) in acetonitrile/triethanolamine (CH 3 CN/TEOA) solutions is provided for the first time by combining experimental and computational approaches. Firstly, we combined the metalation of the porphyrin linkers and the synthesis under microwave conditions of nano-sized materials (150–200 nm) to reach one of the highest CO 2 RR activities under visible light irradiation reported so far for a MOF-based catalyst in terms of formate production (identified in all cases as the sole product), i.e., 6000 μmol g –1 after 4 h for the NanoMOF-545(Fe). A thorough mechanistic study of CO 2 RR is provided afterwards, which elucidated the respective roles of TEOA, porphyrin linkers and Zr 6 -nodes. Photophysical measurements of both metalated and unmetalated MOFs excluded the prevailing belief of ligand-to-Zr 6 cluster charge-transfer state formation, while bulk photolysis proved that the porphyrinic linkers of the MOF promote the photooxidation of TEOA under catalytic conditions. DFT calculations allowed characterization with atomistic detail of a novel reaction mechanism whereby TEOA˙ radicals generated photochemically at the porphyrinic linkers play the crucial role of transferring a formal hydride to a CO 2 molecule activated on a Zr IV center, which acts as a Lewis acid. Notably, this mechanism backed by additional experimental assays explains the experimental activity trends observed upon metalation, on the basis of the ability of the materials to accomplish the photo-oxidation of TEOA. Here, while elucidating the reaction pathways at work in Zr 6 -based MOFs with chromophore linkers, the findings reported herein pinpoint new mechanistic features capable of rationalizing other light-driven reactions making use of TEOA (or structurally related donors) and ultimately, inspire the bottom-up design of new catalysts and catalytic routes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2023

Far-Infrared Line Emission from the Outer Galaxy Cluster Gy 3–7 With SOFIA/FIFI-LS: Physical Conditions and UV Fields

Context. Far-infrared (FIR) line emission provides key information about the gas cooling and heating due to shocks and UV radiation associated with the early stages of star formation. Gas cooling via FIR lines might, however, depend on metallicity. Aims. We aim to quantify the FIR line emission and determine the spatial distribution of the CO rotational temperature, ultraviolet (UV) radiation field, and H2 number density toward the embedded cluster Gy 3–7 in the CMa–l224 star-forming region, whose metallicity is expected to be intermediate between that of the Large Magellanic Cloud and the Solar neighborhood. By comparing the total luminosities of CO and [O I] toward Gy 3–7 with values found for low- and high-mass protostars extending over a broad range of metallicities, we also aim to identify the possible effects of metallicity on the FIR line cooling within our Galaxy. Methods. We studied SOFIA/FIFI-LS spectra of Gy 3–7, covering several CO transitions from J = 14–13 to 31-30, the OH doublet at 79 µm, the [O I] 63.2 and 145.5 µm, and the [C II] 158 µm lines. The field of view covers a 2 0 × 1 0 region with a resolution of ∼7 00–1800 . Results. The spatial extent of CO high-J (Jup ≥14) emission resembles that of the elongated 160 µm continuum emission detected with Herschel, but its peaks are offset from the positions of the dense cores. The [O I] lines at 63.2 µm and 145.5 µm follow a similar pattern, but their peaks are found closer to the positions of the cores. The CO transitions from J = 14–13 to J = 16–15 are detected throughout the cluster and show a median rotational temperature of 170 ± 30 K on Boltzmann diagrams. Comparisons to other protostars observed with Herschel show a good agreement with intermediate-mass sources in the inner Galaxy. Assuming an origin of the [O I] and high-J CO emission in UV-irradiated C−shocks, we obtained pre-shock H2 number densities of 104–105 cm−3 and UV radiation field strengths of 0.1–10 Habing fields (G0). Conclusions. Far-IR line observations reveal ongoing star formation in Gy 3–7, dominated by intermediate-mass Class 0/I young stellar objects. The ratio of molecular-to-atomic far-IR line emission shows a decreasing trend with bolometric luminosities of the protostars. However, it does not indicate that the low-metallicity has an impact on the line cooling in Gy 3–7.

stars: formation↗
DOE OSTI2022

Programmable Photoluminescence via Intrinsic and DNA-Fluorophore Association in a Mixed Cluster Heterometallic MOF

In this report a rapid and facile design strategy to create a highly complex optical tag with programmable, multimodal photoluminescent properties is described. This was achieved via intrinsic and DNA-fluorophore hidden signatures. As a first covert feature of the tag, an intricate novel heterometallic near-infrared (NIR)-emitting mesoporous metal–organic framework (MOF) was designed and synthesized. The material is constructed from two chemically distinct, homometallic hexanuclear clusters based on Nd and Yb. Uniquely, the Nd-based cluster is observed here for the first time in a MOF and consists of two staggered Nd μ3-oxo trimers. To generate controlled, multimodal, and tailorable emission with difficult to counterfeit features, the NIR-emissive MOF was post-synthetically modified via a fluorescent DNA oligo labeling design strategy. The surface attachment of several distinct fluorophores, including the simultaneous attachment of up to three distinct fluorescently labeled oligos was achieved, with excitation and emission properties across the visible spectrum (480-800 nm). The DNA inclusion as a secondary covert element in the tag was demonstrated via the detection of SYBR Gold dye association. Importantly, the approach implemented here serves as a rapid and tailorable way to encrypt distinct information in a facile and modular fashion and provides an innovative technology in the quest toward complex optical tags.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

THE AGES OF 55 GLOBULAR CLUSTERS AS DETERMINED USING AN IMPROVED ΔV{sup HB}{sub TO} METHOD ALONG WITH COLOR-MAGNITUDE DIAGRAM CONSTRAINTS, AND THEIR IMPLICATIONS FOR BROADER ISSUES

Ages have been derived for 55 globular clusters (GCs) for which Hubble Space Telescope Advanced Camera for Surveys photometry is publicly available. For most of them, the assumed distances are based on fits of theoretical zero-age horizontal-branch (ZAHB) loci to the lower bound of the observed distributions of HB stars, assuming reddenings from empirical dust maps and metallicities from the latest spectroscopic analyses. The age of the isochrone that provides the best fit to the stars in the vicinity of the turnoff (TO) is taken to be the best estimate of the cluster age. The morphology of isochrones between the TO and the beginning part of the subgiant branch (SGB) is shown to be nearly independent of age and chemical abundances. For well-defined color-magnitude diagrams (CMDs), the error bar arising just from the 'fitting' of ZAHBs and isochrones is ≈ ± 0.25 Gyr, while that associated with distance and chemical abundance uncertainties is ∼ ± 1.5-2 Gyr. The oldest GCs in our sample are predicted to have ages of ≈13.0 Gyr (subject to the aforementioned uncertainties). However, the main focus of this investigation is on relative GC ages. In conflict with recent findings based on the relative main-sequence fitting method, which have been studied in some detail and reconciled with our results, ages are found to vary from mean values of ≈12.5 Gyr at [Fe/H] ∼< – 1.7 to ≈11 Gyr at [Fe/H] ∼> –1. At intermediate metallicities, the age-metallicity relation (AMR) appears to be bifurcated: one branch apparently contains clusters with disk-like kinematics, whereas the other branch, which is displaced to lower [Fe/H] values by ≈0.6 dex at a fixed age, is populated by clusters with halo-type orbits. The dispersion in age about each component of the AMR is ∼ ± 0.5 Gyr. There is no apparent dependence of age on Galactocentric distance (R{sub G}) nor is there a clear correlation of HB type with age. As previously discovered in the case of M3 and M13, subtle variations have been found in the slope of the SGB in the CMDs of other metal-poor ([Fe/H] ∼< – 1.5) GCs. They have been tentatively attributed to cluster-to-cluster differences in the abundance of helium. Curiously, GCs that have relatively steep 'M13-like' SGBs tend to be massive systems, located at small R{sub G}, that show the strongest evidence of in situ formation of multiple stellar populations. The clusters in the other group are typically low-mass systems (with 2-3 exceptions, including M3) that, at the present time, should not be able to retain the matter lost by mass-losing stars due either to the development of GC winds or to ram-pressure stripping by the halo interstellar medium. The apparent separation of the two groups in terms of their present-day gas retention properties is difficult to understand if all GCs were initially ∼20 times their current masses. The lowest-mass systems, in particular, may have never been massive enough to retain enough gas to produce a significant population of second-generation stars. In this case, the observed light element abundance variations, which are characteristic of all GCs, were presumably present in the gas out of which the observed cluster stars formed.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Influence of Domain Size and Support Composition on the Reducibility of SiO 2 and TiO 2 Supported Tungsten Oxide Clusters

Supported tungsten oxides are widely used in a variety of catalytic reactions. Depending on the support, the cluster size, oxidation state, reducibility and speciation of the tungsten oxides can widely differ. When promoted with a platinum group metal, the resulting spillover of hydrogen may facilitate the reduction of supported tungsten oxide species, depending on the support. High resolution scanning transmission electron microscopy imaging showed nanometer scale WO x clusters were synthesized on SiO 2 whereas highly dispersed species were formed on TiO 2 . Results from H 2 -temperature-programmed reduction showed the presence of Pd lowered the initial reduction temperature of SiO 2 -supported WO x species but interestingly did not affect that of TiO 2 -supported WO x . X-ray photoelectron and absorption spectroscopies showed the W atoms in SiO 2 -supported WO x species reduce from a +6 oxidation state to primarily +5 after thermal treatment in 5% H 2 , while the fraction of W in the +5 oxidation state was relatively unaffected by reduction treatment of TiO 2 -supported WO x . The unusual behavior of TiO 2 -supported WO x was explained by quantum chemical calculations that reveal the lack of change in the oxidation state of W is attributed to charge delocalization on the surface atoms of the titania support, which does not occur on silica. Moreover, modeling results at <600 K in the presence of H 2 suggest the formation of Brønsted acid sites, and the absence of Lewis acid sites, on larger aggregates of WO x on silica and all cluster sizes on titania. These results provide experimental and theoretical insights into the nature of supported tungsten oxide clusters under conditions relevant to various catalytic reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

GHOSTS I: A new faint very isolated dwarf galaxy at D = 12 ± 2 Mpc

We report the discovery of a new faint dwarf galaxy, GHOSTS I, using HST/ACS data from one of our GHOSTS (Galaxy Halos, Outer disks, Substructure, Thick disk, and Star clusters) fields. Its detected individual stars populate an approximately 1 mag range of its luminosity function (LF). Using synthetic color-magnitude diagrams (CMDs) to compare with the galaxy's CMD, we find that the colors and magnitudes of GHOSTS I's individual stars are most consistent with being young helium-burning and asymptotic giant branch stars at a distance of ∼12 ± 2 Mpc. Morphologically, GHOSTS I appears to be actively forming stars, so we tentatively classify it as a dwarf irregular (dIrr) galaxy, although future Hubble Space Telescope (HST) observations deep enough to resolve a larger magnitude range in its LF are required to make a more secure classification. GHOSTS I's absolute magnitude is M{sub V}∼−9.85{sub −0.33}{sup +0.40}, making it one of the least luminous dIrr galaxies known, and its metallicity is lower than [Fe/H] = –1.5 dex. The half-light radius of GHOSTS I is 226 ± 38 pc and its ellipticity is 0.47 ± 0.07, similar to Milky Way and M31 dwarf satellites at comparable luminosity. There are no luminous massive galaxies or galaxy clusters within ∼4 Mpc from GHOSTS I that could be considered as its host, making it a very isolated dwarf galaxy in the local universe.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

EVIDENCE FOR ENRICHMENT BY SUPERNOVAE IN THE GLOBULAR CLUSTER NGC 6273

In our recent investigation, we showed that narrowband photometry can be combined with low-resolution spectroscopy to effectively search for globular clusters (GCs) with supernova (SN) enrichments. Here we apply this technique to the metal-poor bulge GC NGC 6273 and find that the red giant branch stars in this GC are clearly divided into two distinct subpopulations with different calcium abundances. The Ca rich subpopulation in this GC is also enhanced in CN and CH, showing a positive correlation between them. This trend is identical to the result we found in M22, suggesting that this might be a ubiquitous nature of GCs more strongly affected by SNe in their chemical evolution. Our results suggest that NGC 6273 was massive enough to retain SN ejecta, which would place this cluster in the growing group of GCs with Galactic building block characteristics, such as ω Centauri and Terzan 5.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Spectroscopic abundances in the open cluster NGC 6819

High-dispersion spectra of 333 stars in the open cluster NGC 6819, obtained using the HYDRA spectrograph on the WIYN 3.5 m telescope, have been analyzed to determine the abundances of iron and other metals from lines in the 400 Å region surrounding the Li 6708 Å line. Our spectra, with signal-to-noise per pixel ranging from 60 to 300, span the luminosity range from the tip of the red giant branch to a point two magnitudes below the top of the cluster turnoff. We derive radial and rotational velocities for all stars, as well as [Fe/H] based on 17 iron lines, [Ca/H], [Si/H], and [Ni/H] in the 247 most probable, single members of the cluster. Input T{sub eff} estimates for model atmosphere analysis are provided by (B−V) colors merged from several sources, with individual reddening corrections applied to each star relative to a cluster mean of E(B−V) = 0.16. Extensive use is made of ROBOSPECT, an automatic equivalent width measurement program; its effectiveness on large spectroscopic samples is discussed. From the sample of likely single members, [Fe/H] = −0.03 ± 0.06, where the error describes the median absolute deviation about the sample median value, leading to internal precision for the cluster below 0.01 dex. The final uncertainty in the cluster abundance is therefore dominated by external systematics due to the temperature scale, surface gravity, and microturbulent velocity, leading to [Fe/H] = −0.02 ± 0.02 for a sub-sample restricted to main sequence and turnoff stars. This result is consistent with our recent intermediate-band photometric determination of a slightly subsolar abundance for this cluster. [Ca/Fe], [Si/Fe], and [Ni/Fe] are determined to be solar within the uncertainties. NGC 6819 has an abundance distribution typical of solar metallicity thin disk stars in the solar neighborhood.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

UNCOVERING THE FORMATION OF ULTRACOMPACT DWARF GALAXIES BY MULTIVARIATE STATISTICAL ANALYSIS

We present a statistical analysis of the properties of a large sample of dynamically hot old stellar systems, from globular clusters (GCs) to giant ellipticals, which was performed in order to investigate the origin of ultracompact dwarf galaxies (UCDs). The data were mostly drawn from Forbes et al. We recalculated some of the effective radii, computed mean surface brightnesses and mass-to-light ratios, and estimated ages and metallicities. We completed the sample with GCs of M31. We used a multivariate statistical technique (K-Means clustering), together with a new algorithm (Gap Statistics) for finding the optimum number of homogeneous sub-groups in the sample, using a total of six parameters (absolute magnitude, effective radius, virial mass-to-light ratio, stellar mass-to-light ratio, and metallicity). We found six groups. FK1 and FK5 are composed of high- and low-mass elliptical galaxies, respectively. FK3 and FK6 are composed of high-metallicity and low-metallicity objects, respectively, and both include GCs and UCDs. Two very small groups, FK2 and FK4, are composed of Local Group dwarf spheroidals. Our groups differ in their mean masses and virial mass-to-light ratios. The relations between these two parameters are also different for the various groups. The probability density distributions of metallicity for the four groups of galaxies are similar to those of the GCs and UCDs. The brightest low-metallicity GCs and UCDs tend to follow the mass-metallicity relation like elliptical galaxies. The objects of FK3 are more metal-rich per unit effective luminosity density than high-mass ellipticals.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Theoretical assessments of Pd–PdO phase transformation and its impacts on H 2 O 2 synthesis and decomposition pathways

The direct synthesis of H 2 O 2 from O 2 and H 2 provides a green pathway to produce H 2 O 2 , a popular industrial oxidant. Here, in this study, we theoretically investigate the effects of Pd oxidation states, coordination environments, and particle sizes on primary H 2 O 2 selectivities, assessed by calculating the ratio of rate constants for the formation of H 2 O 2 (via OOH* reduction; k O–H ) and the decomposition of OOH* (via O–O cleavage; k O–O ). For Pd metals, the k O–H /k O–O ratio decreased from 10 -4 for Pd(111) to 10 -10 for the Pd 13 cluster at 300 K, indicating poorer H 2 O 2 selectivity as Pd particle size decreases and low primary selectivities for H 2 O 2 overall. As the oxygen chemical potential increases and metals form surface and bulk oxides, the perturbation of Pd–Pd ensemble sites by lattice O atoms results in selectivities that become dramatically higher than unity. For instance, at 300 K, the k O–H /k O–O ratio increases significantly from 10 -4 to 10 9 to 10 16 as Pd(111) oxidizes to Pd 5 O 4 /Pd(111) and to PdO(100), respectively. In contrast, such selectivity enhancements are not observed for surface and bulk oxides that persistently contain rows of more metallic, undercoordinated Pd–Pd ensemble sites, such as PdO(101)/Pd(100) and PdO(101). These Pd–Pd ensembles are also absent when smaller Pd nanoparticles fully oxidize, indicating that smaller PdO clusters can be more selective for H 2 O 2 synthesis. These trends for primary H 2 O 2 selectivities were found to inversely correlate with trends for H 2 O 2 decomposition rates via O–O bond cleavage, demonstrating that catalysts with high primary H 2 O 2 selectivity can also hinder H 2 O 2 decomposition. Ab initio thermodynamic calculations are used to estimate the thermodynamically favored phase among Pd, PdO/Pd and PdO in O 2 , H 2 O 2 /H 2 O, and O 2 /H 2 environments. These results are combined to show that smaller Pd nanoparticles are more prone to be oxidized at lower oxygen chemical potentials, upon which they become more selective than larger Pd particles for H 2 O 2 synthesis.

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

Evolution of Structure and Magnetism in FeCl 2 and FeCl 3 : From Clusters to Monolayers

In this work, we address one of the most fundamental questions in cluster science─how do the structure and properties evolve from clusters to crystals? Using density functional theory (DFT), we focus our study on the evolution of structure and magnetism in iron-chloride systems, from clusters to monolayers. The choice of this system is motivated by the recent experimental confirmation of one of the author’s earlier theoretical prediction that the FeCl 2 cluster is magnetic with a spin magnetic moment of 4 μ B localized at the Fe site, while its dimer, Fe 2 Cl 4 , is antiferromagnetic. Similarly, FeCl 3 cluster is magnetic with a total spin magnetic moment of 5 μ B , with 4 μ B localized at the Fe site and 1 μ B distributed over the Cl sites. The dimer clusters Fe 2 Cl 4 and Fe 2 Cl 6 have an antiferromagnetic ground state, and upon Li-functionalization, both can be magnetically transformed from antiferromagnetic to ferromagnetic states. In contrast, FeCl 2 and FeCl 3 monolayers exhibit different magnetic ground states in their periodic forms: FeCl 2 is ferromagnetic (FM), but in FeCl 3 , the antiferromagnetic (AFM) and FM states are energetically nearly degenerate. Such a difference arises due to the different chemical coordination of the Fe atoms with the Cl atoms, caused by their different oxidation states, which is +2 in FeCl 2 and +3 in FeCl 3 , respectively. Interestingly, Li-functionalization allows both FeCl 3 and FeCl 2 monolayers to be ferromagnetic. Our study highlights that several, but not all, electronic and magnetic characteristics of isolated clusters are preserved in the extended periodic structures. This systematic investigation of iron-halide clusters is expected to inspire further experimental and theoretical exploration into the magnetism of other transition metal halides.

cluster chemistry↗
DOE OSTI2017

Self-consistent clustering analysis: an efficient multiscale scheme for inelastic heterogeneous materials

A predictive computational theory is shown for modeling complex, hierarchical materials ranging from metal alloys to polymer nanocomposites. The theory can capture complex mechanisms such as plasticity and failure that span across multiple length scales. This general multiscale material modeling theory relies on sound principles of mathematics and mechanics, and a cutting-edge reduced order modeling method named self-consistent clustering analysis (SCA) [Zeliang Liu, M.A. Bessa, Wing Kam Liu, “Self-consistent clustering analysis: An efficient multi-scale scheme for inelastic heterogeneous materials,” Comput. Methods Appl. Mech. Engrg. 306 (2016) 319–341]. SCA reduces by several orders of magnitude the computational cost of micromechanical and concurrent multiscale simulations, while retaining the microstructure information. This remarkable increase in efficiency is achieved with a data-driven clustering method. Computationally expensive operations are performed in the so-called offline stage, where degrees of freedom (DOFs) are agglomerated into clusters. The interaction tensor of these clusters is computed. In the online or predictive stage, the Lippmann-Schwinger integral equation is solved cluster-wise using a self-consistent scheme to ensure solution accuracy and avoid path dependence. To construct a concurrent multiscale model, this scheme is applied at each material point in a macroscale structure, replacing a conventional constitutive model with the average response computed from the microscale model using just the SCA online stage. A regularized damage theory is incorporated in the microscale that avoids the mesh and RVE size dependence that commonly plagues microscale damage calculations. The SCA method is illustrated with two cases: a carbon fiber reinforced polymer (CFRP) structure with the concurrent multiscale model and an application to fatigue prediction for additively manufactured metals. For the CFRP problem, a speed up estimated to be about 43,000 is achieved by using the SCA method, as opposed to FE2, enabling the solution of an otherwise computationally intractable problem. The second example uses a crystal plasticity constitutive law and computes the fatigue potency of extrinsic microscale features such as voids. This shows that local stress and strain are capture sufficiently well by SCA. This model has been incorporated in a process-structure-properties prediction framework for process design in additive manufacturing.

Liu, Z.↗
DOE OSTI2017

Magnifying the Early Episodes of Star Formation: Super Star Clusters at Cosmological Distances

We study the spectrophotometric properties of a highly magnified (μ≃40--70) pair of stellar systems identified at z = 3.2222 behind the Hubble Frontier Field galaxy cluster MACS J0416. Five multiple images (out of six) have been spectroscopically confirmed by means of VLT/MUSE and VLT/X-Shooter observations. Each image includes two faint (m{sub UV}≃30.6), young (≲100 Myr), low-mass (<10{sup 7} M{sub ⊙}), low-metallicity (12 + Log(O/H) ≃ 7.7, or 1/10 solar), and compact (30 pc effective radius) stellar systems separated by ≃300 pc after correcting for lensing amplification. We measured several rest-frame ultraviolet and optical narrow (σ{sub v}≲25 km s{sup −1}) high-ionization lines. These features may be the signature of very hot (T>50,000 K) stars within dense stellar clusters, whose dynamical mass is likely dominated by the stellar component. Remarkably, the ultraviolet metal lines are not accompanied by Lyα emission (e.g., C iv/Lyα > 15), despite the fact that the Lyα line flux is expected to be 150 times brighter (inferred from the Hβ flux). A spatially offset, strongly magnified (μ>50) Lyα emission with a spatial extent ≲7.6 kpc{sup 2} is instead identified 2 kpc away from the system. The origin of such a faint emission could be the result of fluorescent Lyα induced by a transverse leakage of ionizing radiation emerging from the stellar systems and/or may be associated with an underlying and barely detected object (with m{sub UV}>34 de-lensed). This is the first confirmed metal-line emitter at such low-luminosity and redshift without Lyα emission—suggesting that, at least in some cases, a non-uniform covering factor of the neutral gas might hamper the Lyα detection.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

An HST/COS survey of the low-redshift intergalactic medium. I. Survey, methodology, and overall results

We use high-quality, medium-resolution Hubble Space Telescope/Cosmic Origins Spectrograph (HST/COS) observations of 82 UV-bright active galactic nuclei (AGNs) at redshifts z{sub AGN} < 0.85 to construct the largest survey of the low-redshift intergalactic medium (IGM) to date: 5138 individual extragalactic absorption lines in H i and 25 different metal-ion species grouped into 2611 distinct redshift systems at z{sub abs} < 0.75 covering total redshift pathlengths Δz{sub H i} = 21.7 and Δz{sub O vi} = 14.5. Our semi-automated line-finding and measurement technique renders the catalog as objectively defined as possible. The cumulative column density distribution of H i systems can be parametrized dN(>N)/dz = C{sub 14}(N/10{sup 14}cm{sup −2}){sup −(β−1)}, with C{sub 14} = 25 ± 1 and β = 1.65 ± 0.02. This distribution is seen to evolve both in amplitude, C{sub 14}∝(1+z){sup 2.3±0.1}, and slope β(z) = 1.75–0.31 z for z ≤ 0.47. We observe metal lines in 418 systems, and find that the fraction of IGM absorbers detected in metals is strongly dependent on N{sub HI}. The distribution of O vi absorbers appears to evolve in the same sense as the Lyα forest. We calculate contributions to Ω{sub b} from different components of the low-z IGM and determine the Lyα decrement as a function of redshift. IGM absorbers are analyzed via a two-point correlation function in velocity space. We find substantial clustering of H i absorbers on scales of Δv = 50–300 km s{sup −1} with no significant clustering at Δv ≳ 1000 km s{sup −1}. Splitting the sample into strong and weak absorbers, we see that most of the clustering occurs in strong, N{sub H i} ≳ 10{sup 13.5} cm{sup −2}, metal-bearing IGM systems. The full catalog of absorption lines and fully reduced spectra is available via the Mikulski Archive for Space Telescopes (MAST) as a high-level science product at http://archive.stsci.edu/prepds/igm/.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Vapor-Phase Fabrication and Condensed-Phase Application of a MOF-Node-Supported Iron Thiolate Photocatalyst for Nitrate Conversion to Ammonium

Herein we describe a method for synthesizing a nitrate reduction catalyst within a metal organic framework (MOF). The MOF NU-1000, a zirconium-based mesoporous material, is exposed by using atomic layer deposition (ALD) to a vaporous iron amidinate coordination complex and subsequently a dodecanethiol ligand to synthesize an iron thiolate cluster grafted on the zirconium oxide nodes. Structural identification of the cluster is conducted through X-ray absorption spectroscopy (XAS) and differential envelope density (DED) analyses. Once submerged in an aqueous solution containing nitrate (30 ppm of N) and irradiated with light, the MOF/iron thiolate cluster assembly can photochemically transform the nitrate to ammonium ions. We suggest that sequential, self-limiting, atomic (metal ion), and molecular (ligand) deposition onto the reactive nodes of chemically and thermally stable MOFs could prove to be a versatile and attractive method for obtaining nature-inspired chemical catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A rigorous non-empirical theoretical analysis of the 2p XPS of NiO: Is it necessary to invoke nonlocal screening?

The role of ligand field effects and many-body effects arising from angular momentum coupling and shake effects for the XPS of NiO, as a representative transition metal oxide, have been investigated using rigorous, non-empirical wave functions for single site cluster models. Here it is shown that important features of the XPS arise from proper treatment of angular momentum coupling and it is unnecessary to invoke non-local screening to explain the experimental XPS. Contrary to the usual understanding, it is shown that inclusion of shake excitations in the many body wavefunctions is responsible for the high BE satellites that are observed. The contribution of covalent mixing of metal and ligand orbitals in the closed shells to screening of core-holes is demonstrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

MODELS FOR METAL-POOR STARS WITH ENHANCED ABUNDANCES OF C, N, O, Ne, Na, Mg, Si, S, Ca, AND Ti, IN TURN, AT CONSTANT HELIUM AND IRON ABUNDANCES

Recent work has shown that most globular clusters have at least two chemically distinct components, as well as cluster-to-cluster differences in the mean [O/Fe], [Mg/Fe], and [Si/Fe] ratios at similar [Fe/H] values. In order to investigate the implications of variations in the abundances of these and other metals for H-R diagrams and predicted ages, grids of evolutionary sequences have been computed for scaled solar and enhanced {alpha}-element metal abundances, and for mixtures in which the assumed [m/Fe] value for each of the metals C, N, O, Ne, Na, Mg, Si, S, Ca, and Ti has been increased, in turn, by 0.4 dex at constant [Fe/H]. These tracks, together with isochrones for ages from Almost-Equal-To 5 to 14 Gyr, have been computed for -3.0 {<=} [Fe/H] {<=}-0.6, with helium abundances Y = 0.25, 0.29, and 0.33 at each [Fe/H] value, using upgraded versions of the Victoria stellar structure program and the Regina interpolation code, respectively. Turnoff luminosity versus age relations from isochrones are found to depend almost entirely on the importance of the CNO cycle, and thereby mainly on the abundance of oxygen. Since C, N, and O, as well as Ne and S, do not contribute significantly to the opacities at low temperatures and densities, variations in their abundances do not impact the predicted T{sub eff} scale of red giants. The latter is a strong function of the abundances of only Mg and Si (and Fe, possibly to a lesser extent) because they are so abundant and because they are strong sources of opacity at low temperatures. For these reasons, Mg and Si also have important effects on the temperatures of main-sequence stars. Due to their low abundances, Na, Ca, and Ti are of little consequence for stellar models. The effects of varying the adopted solar metals mixture and the helium abundance at a fixed [Fe/H] are also briefly discussed.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Impact of Transition Metal Doping on the Structural and Optical Properties of Halide Perovskites

Metal ion doping into halide perovskite materials is a promising approach to enhance long-term film stability and improve solar cell performance. Moreover, the idea of doping metals into halide perovskites is also driven by applications in heterogeneous catalysis. Here, we investigate the incorporation of the transition metals Pt and Pd into mixed-halide perovskite materials. We find that Pt aggregates in large clusters in iodine- and bromine-rich perovskite film compositions, whereas Pd incorporation depends on the underlying bromine to iodine ratio. Furthermore, by using optical and structural characterization methods, we observe that phase segregation in the perovskite layer is suppressed upon doping of either of these metals into the material. This approach further shows the potential to obtain catalytically active halide perovskite films in which the perovskite can serve as a host matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗