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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis

Many metal organic frameworks (MOFs) incorporate metal oxide clusters as nodes. Node sites where linkers are missing can be catalytic sites. We now show how to dial in the number and occupancy of such sites in MIL-53 and MIL-68, which incorporate aluminum-oxide-like nodes. Here, the methods involve modulators used in synthesis and postsynthesis reactions to control the modulator-derived groups on these sites. We illustrate the methods using formic acid as a modulator, giving formate ligands on the sites, and these can be removed to leave μ 2 -OH groups and open Lewis acid sites. Methanol dehydration was used as a catalytic reaction to probe these sites, with infrared spectra giving evidence of methoxide ligands as reaction intermediates. Control of node surface chemistry opens the door for placement of a variety of ligands on a wide range of metal oxide cluster nodes for dialing in reactivity and catalytic properties of a potentially immense class of structurally well-defined materials.

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

Role of Capping Agents in the Synthesis of Salicylate-Capped Zinc Oxide Nanoparticles

Capping agents are often used for controlling the size, aggregation, and properties of nanoparticles. To guide the design of improved nanomaterials for targeted performance, one can use mechanistic insights into the interactions between capping agents and nanoparticles. Here, we employ density functional theory (DFT), reactive force-field molecular dynamics (ReaxFF MD) simulations, and optical spectroscopy to study the interactions between salicylate, as a model capping agent, and zinc oxide (ZnO) nanoparticles. In this work, we find that salicylate strongly interacts with the nanoparticle via the formation of O–Zn bonds in a distorted six-membered coordination ring structure. We describe the mechanisms of capping of ZnO nanoparticles by salicylate via three different binding modes. Simulations indicate that salicylate undergoes dissociative adsorption at the highly active surface Zn sites via a hydrogen-transfer process, thereby forming a tridentate configuration. The water-mediated interaction also facilitates the dissociative adsorption, leading to two salicylate O atoms coordinating with a surface Zn atom, while the other salicylate O atom bonds with another surface Zn atom. For molecular adsorption, binding free energies indicate that salicylate binds more strongly to ZnO, often in a bidentate configuration, than water does. The formation of the salicylate–ZnO complex is substantiated by UV–visible and Fourier transform infrared spectra. We find that the C=O stretching mode of salicylate becomes softened when it interacts with the nanoparticle, suggesting chemisorption of salicylate on ZnO. Although DFT predicts strong interaction between salicylate and ZnO, ReaxFF MD simulation indicates the moderate interaction between these two components in aqueous solution. Water molecules in close contact with the nanoparticle surface undergo dissociation, thus resulting in a surface hydroxyl, a reactive oxygen species that may influence the nanoparticle’s catalytic properties. Overall, the atomic-level information provided here can guide the selection process of salicylate as an appropriate agent for ZnO nanoparticle synthesis when strong interactions of particles with capping agents are required.

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

Dehydration of Methyl Lactate on Alkali Cation-Exchanged Faujasite: Effects of Metal Cation Identity and Water Pressure

Turnover rates for the catalytic dehydration of methyl lactate (ML) over ion-exchanged faujasite (FAU) catalysts depend on the identity of alkali metal cations (Na + , K + , Cs + ) and local solvation effects. Analysis of rate measurements and in situ infrared spectroscopy gives evidence that the reaction involves kinetically relevant dissociation of adsorbed methyl lactate upon alkali metal cations. This process involves concerted methyl transfer to the surface and dissociation of the alkali metal from the framework, which occurs at cationic active sites that remain predominantly unoccupied under relevant conditions (0.5–10 kPa ML, 0.5–15 kPa H 2 O, 563–583 K). Despite the mechanistic similarities, apparent activation enthalpies (ΔH app ‡ ) decrease linearly (47 kJ mol –1 from Na + to Cs + ) with ionization energy and cationic radius, and apparent activation entropies (ΔS app ‡ ) decrease 74 J mol –1 K –1 . These trends reflect electrostatic interactions that stabilize the cations to the anionic sites on the zeolite: stronger association between these charges leads to increasingly endothermic processes to displace the alkali metal to form a cationic methoxy and an intrapore metal lactate intermediate. Water physisorption measurements suggest alkali metal ions bind superstoichiometric quantities of water within FAU pores, and in situ infrared spectra suggest the concerted adsorption of ML requires reorganization of this water. Consequently, these processes introduce entropic gains that partially offset entropy losses associated with ML adsorption. Hence, turnover rates differ only by a factor of 2 among Na-, K-, and Cs-FAU at 573 K (ΔΔG app ‡ = 5 kJ mol –1 ). These findings demonstrate the interplay of alkali metal ions with zeolite active sites and intrapore water clusters for ML dehydration, indicating that these interactions can be leveraged to deliver optimal performance under different reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Vibrational fingerprints of ferroelectric HfO 2

Hafnia (HfO 2 ) is a promising material for emerging chip applications due to its high-κ dielectric behavior, suitability for negative capacitance heterostructures, scalable ferroelectricity, and silicon compatibility. The lattice dynamics along with phononic properties such as thermal conductivity, contraction, and heat capacity are under-explored, primarily due to the absence of high quality single crystals. Herein, we report the vibrational properties of a series of HfO 2 crystals stabilized with yttrium (chemical formula HfO2: xY, where x = 20, 12, 11, 8, and 0%) and compare our findings with a symmetry analysis and lattice dynamics calculations. We untangle the effects of Y by testing our calculations against the measured Raman and infrared spectra of the cubic, antipolar orthorhombic, and monoclinic phases and then proceed to reveal the signature modes of polar orthorhombic hafnia. This work provides a spectroscopic fingerprint for several different phases of HfO 2 and paves the way for an analysis of mode contributions to high-κ dielectric and ferroelectric properties for chip technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A lanthanide-rich kilonova in the aftermath of a long gamma-ray burst

Observationally, kilonovae are astrophysical transients powered by the radioactive decay of nuclei heavier than iron, thought to be synthesized in the merger of two compact objects. Over the first few days, the kilonova evolution is dominated by a large number of radioactive isotopes contributing to the heating rate. On timescales of weeks to months, its behaviour is predicted to differ depending on the ejecta composition and the merger remnant. Previous work has shown that the kilonova associated with gamma-ray burst 230307A is similar to kilonova AT2017gfo, and mid-infrared spectra revealed an emission line at 2.15 micrometres that was attributed to tellurium. Here, in this study, we report a multi-wavelength analysis, including publicly available James Webb Space Telescope data and our own Hubble Space Telescope data, for the same gamma-ray burst. We model its evolution up to two months after the burst and show that, at these late times, the recession of the photospheric radius and the rapidly decaying bolometric luminosity (L bol ∝ t −2.7±0.4 , where t is time) support the recombination of lanthanide-rich ejecta as they cool.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Transformation of atomically dispersed platinum in SAPO-37 into platinum clusters: catalyst for ethylene hydrogenation

Atomically dispersed supported platinum catalysts were synthesized by the reaction of Pt(acac) 2 (acac = acetylacetonato) with the silicoaluminophosphate molecular sieve SAPO-37, with infrared spectra showing that the reaction involved SAPO OH groups. Extended X-ray absorption fine structure (EXAFS) spectra show that, after heating in air to 623 K, each platinum atom on average was bonded to approximately two oxygen atoms of the SAPO support, with no evidence of platinum clusters. X-ray absorption near edge spectra (XANES) indicate a platinum formal oxidation state of approximately +2. Here, these supported mononuclear species lacked catalytic activity for ethylene hydrogenation at 1 bar and room temperature, but activity arose during catalysis in a once-through flow reactor/X-ray absorption spectroscopy cell, as the XANES white line intensity decreased, indicating reduction of the platinum, and the EXAFS-determined Pt–Pt coordination number (CN) increased from essentially zero to 2.7 ± 0.5 after 2 h, indicating the formation of platinum clusters of only a few atoms each. The data indicate the almost instantaneous formation of the clusters and identify them as the catalytically active species. Subsequent exposure of the catalyst to ethylene as in situ EXAFS and XANES data were recorded led to a decrease in the Pt–Pt coordination number to 1.6 ± 0.3 and an increase in the white line intensity, indicating partial oxidative fragmentation of the clusters by ethylene. Platinum clusters in SAPO-37 formed in separate experiments by exposure to H 2 prior to catalysis were also catalytically active for ethylene hydrogenation. Here, the data thus show how to dial in the catalytic activity by forming platinum clusters by exposure of mononuclear platinum to H 2 and how to dial back the activity by oxidative fragmentation of the clusters by reaction with ethylene, all under mild conditions; the ethylene : H 2 ratio of the reactant gas determines the average platinum nuclearity and thus the catalytic activity.

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

Support modification by phosphonic acid ligands controls ethylene hydroformylation on single-atom rhodium sites

To investigate the ability of surface-bound ligands to control activity toward ethylene hydroformylation, we modified site-isolated Rh 1 /TiO 2 with a series of substituted benzyl phosphonic acids. We found that modification of the support by phosphonic acids reduced break-in times for hydroformylation by 4× and increased absolute hydroformylation activity by up to 18× compared to unmodified catalyst at 150 °C. All functionalized catalysts improved hydroformylation activity by at least 9× and improved selectivity by between 7× and 60× relative to the unmodified catalyst. Carbon monoxide probe–molecule spectroscopy indicated that the enhancements in activity among modified samples were due to changes in the local environment of the active Rh site. Specifically, the bite angle of adsorbed carbon monoxide, as determined from infrared spectra, correlated with hydroformylation activity. These findings demonstrate that Rh 1 active sites are highly sensitive to modification of the support with organic ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

CAPOS: The bulge Cluster APOgee Survey: III. Spectroscopic tomography of Tonantzintla 2

Here, we performed the first detailed spectral analysis of red giant members of the relatively high-metallicity globular cluster (GC) Tononzintla 2 (Ton 2) using high-resolution near-infrared spectra collected with the Apache Point Observatory Galactic Evolution Experiment II survey (APOGEE-2), obtained as part of the bulge Cluster APOgee Survey. We investigated chemical abundances for a variety of species including the light, odd-Z, α-, Fe-peak, and neutron-capture elements from high S/N spectra of seven giant members. The derived mean cluster metallicity is [Fe/H] = –0.70 ± 0.05, with no evidence for an intrinsic metallicity spread. Ton 2 exhibits a typical α-enrichment that follows the trend for high-metallicity Galactic GCs, similar to that seen in 47 Tucanae and NGC 6380. We find a significant nitrogen spread (> 0.87 dex), and a large fraction of nitrogen-enriched stars that populate the cluster. Given the relatively high-metallicity of Ton 2, these nitrogen-enriched stars are well above the typical Galactic levels, indicating the prevalence of the multiple-population phenomenon in this cluster that also contains several stars with typical low first-generation N abundances. We also identify the presence of [Ce/Fe] abundance spread in Ton 2, which is correlated with the nitrogen enhancement, indicating that the s-process enrichment in this cluster has likely been produced by relatively low-mass asymptotic giant branch stars. Furthermore, we find a mean radial velocity of the cluster, –178.6 ± 0.86 km s –1 , with a small velocity dispersion, 2.99 ± 0.61 km s –1 , which is typical of GCs. We also find a prograde bulge-like orbit for Ton 2 that appears to be radial and highly eccentric. Finally, the considerably nitrogen-enhanced population observed in Ton 2, combined with its dynamical properties, makes this object a potential progenitor for the nitrogen-enriched field stars identified so far toward the bulge region at similar metallicity.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Performant automatic differentiation of local coupled cluster theories: Response properties and ab initio molecular dynamics

In this work, we introduce a differentiable implementation of the local natural orbital coupled cluster (LNO-CC) method within the automatic differentiation framework of the PySCFAD package. The implementation is comprehensively tuned for enhanced performance, which enables the calculation of first-order static response properties on medium-sized molecular systems using coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. We evaluate the accuracy of our method by benchmarking it against the canonical CCSD(T) reference for nuclear gradients, dipole moments, and geometry optimizations. In addition, we demonstrate the possibility of property calculations for chemically interesting systems through the computation of bond orders and Mössbauer spectroscopy parameters for a [NiFe]-hydrogenase active site model, along with the simulation of infrared spectra via ab initio LNO-CC molecular dynamics for a protonated water hexamer.

Chemistry↗
DOE OSTI2021

The first spectroscopically confirmed brown dwarfs in NGC 2264

ABSTRACT We present spectroscopic follow-up observations of 68 red, faint candidates from our multi-epoch, multiwavelength, previously published survey of NGC 2264. Using near-infrared spectra from VLT/KMOS, we measure spectral types and extinction for 32 young low-mass sources. We confirm 13 as brown dwarfs in NGC 2264, with spectral types between M6 and M8, corresponding to masses between 0.02 and 0.08 M⊙. These are the first spectroscopically confirmed brown dwarfs in this benchmark cluster. 19 more objects are found to be young M-type stars of NGC 2264 with masses of 0.08–0.3 M⊙. 7 of the confirmed brown dwarfs as well as 15 of the M-stars have IR excess caused by a disc. Comparing with isochrones, the typical age of the confirmed brown dwarfs is <0.5–5 Myr. More than half of the newly identified brown dwarfs and very low-mass stars have ages <0.5 Myr, significantly younger than the bulk of the known cluster population. Based on the success rate of our spectroscopic follow-up, we estimate that NGC 2264 hosts 200–600 brown dwarfs in total (in the given mass range). This would correspond to a star-to-brown dwarf ratio between 2.5:1 and 7.5:1. We determine the slope of the substellar mass function as $\alpha = 0.43^{+0.41}_{-0.56}$; these values are consistent with those measured for other young clusters. This points to a uniform substellar mass function across all star-forming environments.

Pearson, Samuel↗
DOE OSTI2021

Large binocular telescope observations of new six compact star-forming galaxies with [Ne v ] λ3426 Å emission

ABSTRACT We report the discovery of [Ne v] λ3426 emission, in addition to He ii λ4686 emission, in six compact star-forming galaxies. These observations considerably increase the sample of eight such galaxies discovered earlier by our group. For four of the new galaxies, the optical observations are supplemented by near-infrared spectra. All galaxies, but one, have H ii regions that are dense, with electron number densities of ∼ 300–700 cm−3. They are all characterized by high H β equivalent widths EW(H β) ∼ 190–520 Å and high O32 = [O iii] λ5007/[O ii] λ3727 ratios of 10–30, indicating young starburst ages and the presence of high ionization radiation. All are low-metallicity objects with 12 + logO/H = 7.46–7.88. The spectra of all galaxies show a low-intensity broad component of the H α line and five of six objects show Wolf–Rayet features. Comparison with photoionization models shows that pure stellar ionization radiation from massive stars is not hard enough to produce such strong [Ne v] and He ii emission in our galaxies. The [Ne v] λ3426/He ii λ4686 flux ratio of ∼1.2 in J1222+3602 is consistent with some contribution of active galactic nucleus ionizing radiation. However, in the remaining five galaxies, this ratio is considerably lower, $\lesssim$ 0.4. The most plausible models are likely to be non-uniform in density, where He ii and [Ne v] lines are emitted in low-density channels made by outflows and illuminated by harder ionizing radiation from radiative shocks propagating through these channels, whereas [O iii] emission originates in denser regions exposed to softer stellar ionizing sources.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

Fundamental effective temperature measurements for eclipsing binary stars – IV. Selection of new benchmark stars and first results for HD 22064

I describe the selection and initial characterization of 20 eclipsing binary stars that are suitable for calibration and testing of stellar models and data analysis algorithms used by the PLATO mission and spectroscopic surveys. The binary stars selected are F-/G-type dwarf stars with M-type dwarf companions that contribute less than 2 per cent of the flux at optical wavelengths. The light curves typically show well-defined total eclipses with very little variability between the eclipses. I have used near-infrared spectra obtained by the APOGEE survey to measure the spectroscopic orbit for both stars in HD 22064. Combined with an analysis of the TESS light curve, I derive the following masses and radii: M 1 = 1.35 ± 0.03M ⊙ , M 2 = 0.58 ± 0.01M ⊙ , R 1 = 1.554 ± 0.014R ⊙ , R 2 = 0.595 ± 0.008R ⊙ . Using R 1 and the parallax from Gaia EDR3, I find that the primary star’s angular diameter is θ = 0.1035 ± 0.0009 mas. The apparent bolometric flux of the primary star is ${\mathcal {F}}_{{\oplus },0} = (7.51\pm 0.09)\times 10^{-9}$ erg cm -2 s -1 . Hence, this F2V star has an effective temperature $T_{\rm eff,1} = 6763{\rm \, K} \pm 39{\rm \, K}$. HD 22064 is an ideal benchmark star that can be used for ‘end-to-end’ tests of the stellar parameters measured by large-scale spectroscopic surveys or stellar parameters derived from asteroseismology with PLATO. The techniques described here for HD 22064 can be applied to the other eclipsing binaries in the sample in order to create an all-sky network of such benchmark stars.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

Environment-imposed selection rules for nuclear-spin conversion of H 2 in molecular crystals

Nuclear-spin conversion in molecular hydrogen is governed by strict symmetry rules that typically require magnetic fields or catalytic surfaces to break. Here we demonstrate that the intrinsic tensor composition of a non-magnetic molecular crystal field can impose and relax these rules without external fields. High-resolution infrared spectra of H 2 in crystalline CO 2 reveal large rank-2 (quadrupolar) crystal-field splittings of the 𝑚 sublevels, while nuclear-spin conversion occurs only through 𝛥𝑚 = 0 channels. Replacing CO 2 with polar N 2 O introduces rank-1 (dipole) components that partially open 𝛥⁢𝑚 ≠ 0 pathways, while incorporation of paramagnetic NO 2 fully lifts the restriction. Furthermore, these results establish a direct correspondence between crystal-field tensor rank and nuclear-spin dynamics, introducing a general symmetry-based framework for designing and controlling spin-isomer populations and quantum-state connectivity in molecular solids.

McLane, Nathan [University of Maryland, College Pa↗
DOE OSTI2020

Deep neural network for the dielectric response of insulators

In this work, we introduce a deep neural network to model in a symmetry preserving way the environmental dependence of the centers of the electronic charge. The model learns from ab initio density functional theory, wherein the electronic centers are uniquely assigned by the maximally localized Wannier functions. When combined with the deep potential model of the atomic potential energy surface, the scheme predicts the dielectric response of insulators for trajectories inaccessible to direct ab initio simulation. The scheme is nonperturbative and can capture the response of a mutating chemical environment. We demonstrate the approach by calculating the infrared spectra of liquid water at standard conditions, and of ice under extreme pressure, when it transforms from a molecular to an ionic crystal.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Supercooled Goldstone Bosons at the QCD Chiral Phase Transition

We discuss a universal nonequilibrium enhancement of long-wavelength Goldstone bosons induced by quenches to the broken phase in Model G—the dynamical universality class of an 𝑂⁡(4) antiferromagnet and the chiral phase transition in QCD. Scaling arguments for the coarsening dynamics describing the formation of the chiral condensate predict a parametric enhancement in the infrared spectra of Goldstone bosons, a prediction confirmed by stochastic simulations of the transition. The details of the enhancement are determined by the nonlinear dynamics of a superfluid effective theory, which is a limit of Model G reflecting the broken 𝑂⁡(4) symmetry. Our results translate to a parametric enhancement of low-momentum pions in heavy-ion collisions at the LHC, which are underpredicted in current hydrodynamic models without critical dynamics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Refined Outgassing Model for the LiH/LiOH System

Previous models for H 2 and H 2 O outgassing from moisture exposed LiH specimens were based on temperature programmed desorption/decomposition (TPD) experiments and analyses that yielded kinetic descriptions which were specific to defined sets of initial conditions. Subsequently the inputs to the kinetic models were refined to correlate with infrared spectra of the adsorbed species. In this current enhancement, better agreement between prediction and experiment was obtained through: 1) refining the reaction mechanisms for some of the decomposition reactions; 2) developing the potential range of kinetic parameters by simultaneous fitting of all the TPD outgassing curves obtained at different heating rates; and, 3) limiting the scope of possible kinetic parameters to an optimized subset by matching the outgassing prediction curves at 3 different temperatures to the outcomes from the accurate but cumbersome, non-intuitive, and effort demanding isoconversional analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Properties of Gaseous Deprotonated L-Cysteine S-Sulfate Anion [cysS-SO3]−: Intramolecular H-Bond Network, Electron Affinity, Chemically Active Site, and Vibrational Fingerprints

L-cysteine S-sulfate, Cys-SSO3H, and their derivatives play essential roles in biological chemistry and pharmaceutical synthesis, yet their intrinsic molecular properties have not been studied to date. In this contribution, the deprotonated anion [cysS-SO3]− was introduced in the gas phase by electrospray and characterized by size-selected, cryogenic, negative ion photoelectron spectroscopy. The electron affinity of the [cysS-SO3]• radical was determined to be 4.95 ± 0.10 eV. In combination with theoretical calculations, it was found that the most stable structure of [cysS-SO3]− (S1) is stabilized via three intramolecular hydrogen bonds (HBs); i.e., one O-H……N between the -COOH and -NH2 groups, and two N-H……O HBs between -NH2 and -SO3, in which the amino group serves as both HB acceptor and donor. In addition, a nearly iso-energetic conformer (S2) with the formation of an O-H……N-H……O-S chain-type binding motif competes with S1 in the source. The most reactive site of the molecule susceptible for electrophilic attacks is the linkage S atom. Theoretically predicted infrared spectra indicate that O-H and N-H stretching modes are the fingerprint region (2800 to 3600 cm−1) to distinguish different isomers. The obtained information lays out a foundation to better understand the transformation and structure–reactivity correlation of Cys-SSO3H in biologic settings.

74 ATOMIC AND MOLECULAR PHYSICS↗