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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

Theoretical studies of the low-lying states of ScO, ScS, VO, and VS

Bonding in the low-lying states of ScO, ScS, VO, and VS is theoretically studied. Excellent agreement is obtained with experimental spectroscopic constants for the low-lying states of ScO and VO. The results for VS and ScS show that the bonding in the oxides and sulfides is similar, but that the smaller electronegativity in S leads to a smaller ionic component in the bonding. The computed D0 of the sulfides are about 86 percent of the corresponding oxides, and the low-lying excited states are lower in the sulfides than in the corresponding oxides. The CPF method is shown to be an accurate and cost-effective method for obtaining reliable spectroscopic constants for these systems.

Bauschlicher, Charles W., Jr.↗
DOE OSTI2024

Disentangling Acid‐Base Chemistry through Blue Shifting Hydrogen Bond Contributions

The blue shifting of vibrational frequencies in hydrogen bonded molecules, as observed in aqueous environments, has been attributed to local partial charge transfer from solvation. Here, in this study, we extrapolate the blue shift model to the stronger ionic interactions between hydrogen bond acceptors associated with protonation through augmented pH levels and competitive interactions with counter ion pairing. The chemical model we utilize in this work is the aqueous pyridine‐pyridinium equilibrium to characterize the blue shifts observed in the pyridinium chloride ionic system. The observed agreement between observed experimental and calculated spectral shifts shows that the blue shifting model can be extrapolated to stronger interactions and accurately describe the nature of the hydrogen bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Global expression for representing cohesive-energy curves. II

Schlosser et al. (1991) showed that the R dependence of the cohesive energy of partially ionic solids may be characterized by a two-term energy relationship consisting of a Coulomb term arising from the charge transfer, delta-Z, and a scaled universal energy function, E*(a *), which accounts for the partially covalent character of the bond and for repulsion between the atomic cores for small R; a* is a scaled length. In the paper by Schlosser et al., the normalized cohesive-energy curves of NaCl-structure alkali-halide crystals were generated with this expression. In this paper we generate the cohesive-energy curves of several families of partially ionic solids with different crystal structures and differing degrees of ionicity. These include the CsCl-structure Cs halides, and the Tl and Ag halides, which have weaker ionic bonding than the alkali halides, and which have the CsCl and NaCl structures, respectively. The cohesive-energy-curve parameters are then used to generate theoretical isothermal compression curves for the Li, Na, K, Cs, and Ag halides. We find good agreement with the available experimental compression data.

Schlosser, Herbert↗
DOE OSTI2019

Diuranium(IV) Carbide Cluster U 2 C 2 Stabilized Inside Fullerene Cages

>Novel actinide cluster fullerenes, U 2 C 2 @ I h (7)-C 80 and U 2 C 2 @ D 3 h (5)-C 78 , were synthesized and fully characterized by mass spectrometry, single-crystal X-ray crystallography, UV–vis–NIR, nuclear magnetic resonance spectroscopy (NMR), X-ray absorption spectroscopy (XAS), Raman spectroscopy, IR spectroscopy, as well as density functional and multireference wave function calculations. The encapsulated U 2 C 2 is a novel example of a uranium carbide cluster featuring two U centers bridged by a C≡C unit. The U–C bond distances in these U 2 C 2 clusters are in the range between 2.130 and 2.421 Å. While the U 2 C 2 cluster in U 2 C 2 @C 80 adopts a butterfly-shaped geometry with a U–C 2 –U dihedral angle of 112.7° and a U–U distance of 3.855 Å, the U–U distance in U 2 C 2 @C 78 is 4.164 Å and the resulting U–C 2 –U dihedral angle is increased to 149.1°. The combined experimental and quantum-chemical results suggest that the formal U oxidation state is +4 in the U 2 C 2 cluster, and each U center transfers three electrons to the C 2 n cage and one electron to C 2 . Different from the strong U ＝ C covalent bonding reported for U 2 C 2 @ C 80 , the U–C bonds in U 2 C 2 are less covalent and predominantly ionic. The C–C triple bond is somewhat weaker than in HCCH, and the C–C π bonds undergo donation bonding with the U centers. This work shows that the combination of the unique encapsulation effect of fullerene cages and the variable oxidation states of actinide elements can lead to the stabilization of novel actinide clusters, which are not accessible by conventional synthetic methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ab initio Geochemistry of Hydrous Phases (Final Report)

Hydrous phases are among the most important Earth components. They are important for a broad suite of Earth processes, including the origin of life. From both thermodynamic and structural perspectives, however, they represent some of the most complex naturally occurring materials: their bonding often includes a combination of covalent solid, weak ionic, van der Waals, and hydrogen bonding, all within large unit cells. Most are solid solutions, and many are prone to variations in layer packing. Thermodynamic modeling of these materials is fundamental for understanding present and past natural processes, including those that shaped—and continue to shape—the structure and evolution of our planet. Yet, the thermodynamic properties of these materials at appropriate conditions are challenging to measure. To make significant progress and attain a deep understanding of these materials requires an atomistic theoretical approach.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Molecular Properties of Thorium Hydrides: Electron Affinities and Thermochemistry

In this work, high-level electronic structure calculations of the ground and low-lying energy electronic states for ThH x and ThH x – for x = 2–5 are reported and compared to available anion photoelectron detachment experiments. The adiabatic electron affinities (EAs) are predicted to be 0.82, 0.88, 0.51, and 2.36 eV for x = 2 to 5, respectively, at the Feller– Peterson–Dixon (FPD) level. The vertical detachment energies (VDEs) are predicted to be 0.84, 0.88, 0.81, and 4.38 eV for x = 2–5, respectively. The corresponding experimental VDEs are 0.871 eV for x = 2, 0.88 eV for x = 3, and 4.09 eV for x = 5. As for ThH, there is a significant spin–orbit (SO) correction for the EA of ThH 2 , and this correction decreases substantially for x > 2. The observed ThH 2 – photoelectron spectrum has many transitions as predicted at the CASPT2-SO level. The FPD bond dissociation energies (BDEs) increase from 67 to 75 kcal/mol for x = 2 to x = 4 at the FPD level. The BDE for ThH 5 is much lower as it is a complex of H 2 with ThH 3 . The hydride affinities for x = 2 to 4 are all comparable and near 70 kcal/mol. A natural bond orbital analysis is consistent with a significant Th + –H– ionic contribution to the Th–H bonds. There is very little participation of the 5f orbitals in the bonding and the valence electrons on the Th are dominated by 7s and 6d for the neutrals and anions except for ThH 2 – where there is a significant contribution from the 7p.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

Mean excitation energies for stopping powers in various materials using local plasma oscillator strengths

The basic model of Lindhard and Scharff, known as the local plasma model, is used to study the effects on stopping power of the chemical and physical state of the medium. Unlike previous work with the local plasma model, in which individual electron shifts in the plasma frequency were estimated empirically, he Pines correction derived for a degenerate Fermi gas is shown herein to provide a reasonable estimate, even on the atomic scale. Thus, the model is moved to a complete theoretical base requiring no empirical adjustments, as characteristic of past applications. The principal remaining error is in the overestimation of the low-energy absorption properties that are characteristic of the plasma model in the region of the atomic discrete spectrum, although higher-energy phenomena are accurately represented, and even excitation-to-ionization ratios are given to fair accuracy. Mean excitation energies for covalent-bonded gases and solids, for ionic gases and crystals, and for metals are calculated using first-order models of the bonded states.

Wilson, J. W.↗
DOE OSTI2022

ThAu 2 – , ThAu 2 O – , and ThAuOH – anions: Photoelectron spectroscopic and theoretical characterization

The thorium–gold negative ions ThAu 2 – , ThAu 2 O – , and ThAuOH – have been observed and experimentally characterized by anion photoelectron spectroscopy. These experiments are accompanied by extensive ab initio electronic structure calculations using a relativistic composite methodology based primarily on coupled cluster singles and doubles with perturbative triples calculations. The theoretical electron affinities (EAs) at 0 K agree with the experimental adiabatic EAs to within 0.02 eV for all species. Two separate isomers were located in the calculations for ThAuOH – , and detachment from both of these appears to be present in the photoelectron spectrum. Excited electronic states of the neutral molecules are reported at the equation of motion-coupled cluster singles and doubles level of theory. Atomization energies and heats of formation are also calculated for each neutral species and have expected uncertainties of 3 and 4 kcal/mol, respectively. The σ bonds between Th and Au are determined by natural bond orbital analysis to consist of predominately sd hybrids on Th bonding with the Au 6s orbital. In order to investigate the correspondence between the bonding in Th–Au and Th–F molecules, a limited number of calculations were also carried out on most of the F-analogs of this study. These results demonstrate that Au does behave like F in these cases, although the Th–F σ bonds are much more ionic compared to Th–Au. This results in an EA for ThF 2 that is 10 kcal/mol smaller than that of ThAu 2 . The EA values for the Th(IV) species, i.e., ThX 2 O and ThXOH, only differed, however, by 3–4 kcal/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

Inorganic Water Repellent Coatings for Thermal Protection Insulation on an Aerospace Vehicle

The objective of this research was two-fold: first, to identify and test inorganic water-repellent materials that would be hydrophobic even after thermal cycling to temperatures above 600 C and, second, to develop a model that would link hydrophobicity of a material to the chemical properties of its constituent atoms. Four different materials were selected for detailed experimental study, namely, boron nitride, talc, molybdenite, and pyrophyllite, all of which have a layered structure made up of ionic/covalent bonds within the layers but with van der Waals bonds between the layers. The materials tested could be considered hydrophobic for a nonporous surface but none of the observed contact angles exceeded the necessary 90 degrees required for water repellency of porous materials. Boron nitride and talc were observed to retain their water-repellency when heated in air to temperatures that did not exceed 800 C, and molybdenite was found to be retain its hydrophobicity when heated to temperatures up to 600 C. For these three materials, oxidation and decomposition were identified to be the main cause for the breakdown of water repellency after repeated thermal cycling. Pyrophyllite shows the maximum promise as a potential water-repellent inorganic material, which, when treated initially at 900 C, retained its shape and remained hydrophobic for two thermal cycles where the maximum retreatment temperature is 900 C. A model was developed for predicting materials that might exhibit hydrophobicity by linking two chemical properties, namely, that the constituent ions of the compound belong to the soft acid-base category and that the fractional ionic character of the bonds be less than about 20 percent.

Fuerstenau, D. W.↗
NASA NTRS1997

Inorganic Water Repellent Coatings for Thermal Protection Insulation on an Aerospace Vehicle

The objective of this research was two-fold: first, to identify and test inorganic water-repellent materials that would be hydrophobic even after thermal cycling to temperatures above 600 C and, second, to develop a model that would link hydrophobicity of a material to the chemical properties of its constituent atoms. Four different materials were selected for detailed experimental study, namely, boron nitride, talc, molybdenite, and pyrophyllite, all of which have a layered structure made up of ionic/covalent bonds within the layers but with van der Waals bonds between the layers. The materials tested could be considered hydrophobic for a nonporous surface but none of the observed contact angles exceeded the necessary 90 degrees required for water repellency of porous materials. Boron nitride and talc were observed to retain their water-repellency when heated in air to temperatures that did not exceed 800 C, and molybdenite was found to be retain its hydrophobicity when heated to temperatures up to 600 C. For these three materials, oxidation and decomposition were identified to be the main cause for the breakdown of water repellency after repeated thermal cycling. Pyrophyllite shows the maximum promise as a potential water-repellent inorganic material, which, when treated initially at 900 C, retained its shape and remained hydrophobic for two thermal cycles where the maximum retreatment temperature is 900 C. A model was developed for predicting materials that might exhibit hydrophobicity by linking two chemical properties, namely, that the constituent ions of the compound belong to the soft acid-base category and that the fractional ionic character of the bonds be less than about 20 percent.

Fuerstenau, D. W.↗
DOE OSTI2024

Amide-Engineered Metal–Organic Porous Liquids Toward Enhanced CO 2 Photoreduction Performance

The development of alternative catalytic systems toward high-performance CO 2 photoreduction is considered to be a promising approach to address the future energy demand and reduce the CO 2 emissions. However, CO 2 molecules are thermodynamically stable in nature, and thus the adsorption and activation of CO 2 on the surface of catalysts are the key factors to determine the conversion efficiency. Herein, a porous liquid (NH 2 -UIO-66 PL) is demonstrated for efficiently facilitating the adsorption and activation of CO 2 by modification of metal–organic framework (NH 2 -UIO-66) with ionic liquid via amide bonds. CdS/NH 2 -UIO-66 PL exhibits high-performance CO 2 -to-CO photoreduction with CO yield of 71.37 µmol g -1 h -1 and selectivity of 100%. Experiments and theoretical calculations show that the introduced amide moieties not only enriched the electron density at Zr 4+ active sites but also stabilize *COOH intermediate. In conclusion, the achievements provide an effective strategy for the development of metal–organic frameworks for energy catalysis.

*COOH reaction pathway↗
DOE OSTI2024

Probing Noncovalent Interaction Strengths of Host-Guest Complexes Using Negative Ion Photoelectron Spectroscopy

Noncovalent interactions (NCIs) are crucial for the formation and stability of host-guest complexes, which have wide-ranging implications across various fields, including biology, chemistry, materials science, pharmaceuticals, and environmental science. However, since NCIs are relatively weak and sensitive to bulk perturbation, direct and accurate measurement of their absolute strength has always been a significant challenge. This concept article aims to demonstrate the gas-phase electrospray ionization (ESI)-negative ion photoelectron spectroscopy (NIPES) as a direct and precise technique to measure the absolute interaction strength, probe nature of NCIs, and reveal the electronic structural information for host-guest complexes. Here, our recent studies in investigating various host-guest complexes that involve various types of NCIs such as anion–π, (di)hydrogen bonding, charge-separated ionic interactions, are overviewed. Finally, a summary and outlook are provided for this field.

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

Deep Eutectic Solvents: A Review of Fundamentals and Applications

Deep eutectic solvents (DESs) are an emerging class of mixtures characterized by significant depressions in melting points compared to those of the neat constituent components. These green materials are promising for applications as inexpensive ’designer’ solvents exhibiting a host of tunable physicochemical properties. Here, a detailed review of the current literature reveals the lack of predictive understanding of the microscopic mechanisms that govern the structure-property relationships in this class of solvents. Complex hydrogen bonding behavior is postulated as the root cause of their melt-ing point depressions and physicochemical properties; to understand these hydrogen bonded networks, it is imperative to study these systems as dynamic entities using both simulations and experiments. This review emphasizes recent research efforts in order to elucidate the next steps needed to develop a fundamental framework for understanding DESs. It covers recent developments in DES research, frames outstanding scientific questions, and identifies gainful research thrusts that would advance the field towards predictive models and fundamental understanding of these solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Unveiling a Novel, Cation-Rich Compound in a High-Pressure Pb–Te Binary System

Because of the common oxidation states of group IV elements (+2 or +4) and group VI elements (–2), 1:1 and 1:2 are two typical stoichiometries found in the IV–VI compounds. Particularly, in the Pb–Te binary system, the 1:1 stoichiometric PbTe is believed to be the only stable compound. Herein, using evolutionary algorithms, density functional theory, a laser-heated diamond anvil cell, and synchrotron X-ray diffraction experiments, we discovered a novel Pb–Te compound with an unexpected stoichiometry of 3:2 above 20 GPa. This tetragonal Pb 3 Te 2 is the one of the very few cation-rich compounds that has ever been discovered in the entire IV–VI binary system. Further analyses based on electron density distribution, electron localization function, and Bader charge have shown that this newly discovered compound has a mixed character of chemical bonding with a decreased ionicity. By further calculating the electron–phonon interaction, Pb 3 Te 2 is predicted to exhibit a superconducting transition at low temperatures. Lastly, the discovery of Pb 3 Te 2 paves the way for further explorations of other novel cation-rich IV–VI group compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Synthesis, structural characterization and luminescence properties of 1-carboxymethyl-3-ethylimidazolium chloride

A microcrystalline carboxyl-functionalized imidazolium chloride, namely 1-carboxymethyl-3-ethylimidazolium chloride, C 7 H 11 N 2 O 2 + ·Cl – , has been synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform IR spectroscopy (ATR-FT-IR), single-crystal X-ray diffraction, thermal analysis (TGA/DSC), and photoluminescence spectroscopy. In the crystal structure, cations and anions are linked by C—H...Cl and C—H...O hydrogen bonds to create a helix along the [010] direction. Adjacent helical chains are further interconnected through O—H...Cl and C—H...O hydrogen bonds to form a (101¯) layer. Finally, neighboring layers are joined together via C—H...Cl contacts to generate a three-dimensional supramolecular architecture. Thermal analyses reveal that the compound melts at 449.7 K and is stable up to 560.0 K under a dynamic air atmosphere. Photoluminescence measurements show that the compound exhibits a blue fluorescence and a green phosphorescence associated with spin-allowed ( 1 π← 1 π*) and spin-forbidden ( 1 π← 3 π*) transitions, respectively. As a result, the average luminescence lifetime was determined to be 1.40 ns for the short-lived ( 1 π← 1 π*) transition and 105 ms for the long-lived ( 1 π← 3 π*) transition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Thermodynamic characterization of synthetic lead-arsenate apatites with different halogen substitutions

Abstract Thermodynamic parameters have been measured for synthetic analogs of the mimetite-group minerals Pb5(AsO4)3X (X = OH, Cl, Br, I) belonging to the apatite supergroup. Phases precipitated from aqueous solutions under ambient conditions with well characterized structures and compositions were studied. For each phase, dissolution enthalpy was experimentally determined by oxide melt drop solution calorimetry in a molten solvent of sodium molybdate (3Na2O·4MoO3) at 976 K. The enthalpy of formation from the elements ΔHf,elo was calculated using thermochemical cycles and was −3030.6 ± 11.5, −3026.6 ± 15.8, −2967.6 ± 25.0, and −2993.1 ± 12.2 kJ/mol for Pb5.00(AsO4)3.00OH0.86(CO3)0.07, Pb5.00(AsO4)3.00Cl0.80(CO3)0.10, Pb5.00(AsO4)3.00Br0.80(CO3)0.10, and Pb5.00(AsO4)3.00I0.45OH0.35(CO3)0.10, respectively. These ΔHf,elo values exhibit typical trends for apatites: they increased (were less negative) with the increasing molar mass and ionic radius of X and decreased with the electronegativity and ionization energy of X. The compilation and comparison of data for Ca-, Pb-, P-, and As-apatites revealed correlations indicating that thermodynamic enthalpic stability is largely influenced by chemical factors (e.g., differences in electronegativities of the elements, ionization energy, or ionic characteristics of the bonds) and to a lesser extent by physical and geometric parameters in the crystal structure related to the mass and size of the X anion. Using the correlations, it was possible to estimate the value of hitherto unknown ΔHf,elo for Pb5(AsO4)3F, −3144.3 ± 66.5 kJ/mol. The observed relationships apply to the entire apatite supergroup and can be used to predict the values of ΔHf,elo for phases that have not been studied experimentally. The new data on environmentally significant phases will contribute to the modeling of mineral-water interactions, particularly for potential use in the remediation of soils and wastes contaminated with Pb and As and in the immobilization of radioactive waste containing I-129.

Geochemistry & Geophysics↗
DOE OSTI2021

Biocompatible Electrostatic Layered Systems for Viral Elimination in the Nose/Throat

An anti-viral coating for the nose & throat is needed to quickly address the spread of COVID-19 infections and to aid future pandemics. Current nasal delivery systems are typically a 1-spray homogenous solution, which is convenient but may not be as efficient or durable as a multi-spray solution that contains a binding layer to anchor the anti-viral components. Many of the current nasal solutions being investigated to aid in pandemic response have solution-based mechanisms of action and are quickly cleared from the nose/mouth limiting their efficacy lifetime. A multi-spray approach utilizing strong intermolecular forces between polymeric materials and anti-viral agents to provide a robust biocompatible coating is expected to have increased physical and chemical properties to combat viral infection. This work evaluated which tailored biocompatible materials are needed to generate a layered system to combat viral infection. This layered system takes advantage of electrostatic interactions to bind anti-viral components, shown in Figure 1. Proof of concept success was demonstrated through cell toxicity studies and anti-viral assays on both the individual layer components and the complete layered system. Project work began with chemical modifications of Xantham Gum to hydrolyzing xanthan gum to give a negatively charged polymer with varying degrees of ionic character and investigate bonding efficiencies. However, this was abandoned in favor of comparing COTS available materials listed in Table 1 (Results section). Concentration and adhesion studies were performed on layers created using the listed polymeric materials and anti-viral agents. Finally, biocompatibility of materials, layers, and coating system were confirmed through cytotoxicity studies and the efficacy of the anti-viral properties tested with phi6 bacteriophage as a SARS-CoV2 surrogate.

36 MATERIALS SCIENCE↗