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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Surface Hydration and Hydroxyl Configurations of Gibbsite and Boehmite Nanoplates

Discontinuation of the bulk structure at the interface between metal oxide particles and water leads to altered bonding characteristics and unique facet-dependent molecular environments. Surface hydration and consequent hydroxylation adds further complexity to the interface, details that for metal (oxy)hydroxides are especially difficult to isolate from the background signal of bulk structural hydroxyls. Here we probe for the first time the hydroxylation and hydration structures on basal surfaces of gibbsite (?-Al(OH)3) and boehmite (?-AlOOH) nanoplates at ambient conditions, using the interface-sensitive technique vibrational sum frequency generation spectroscopy (VSFG). Hydroxyl stretching modes at the interfaces with adsorbed water layers compared directly to Raman and infrared bulk modes show that while gibbsite surface frequencies were sharp and nearly identical to those in the bulk, boehmite surface hydroxyls displayed a very different broad spectrum of states. Ab initio molecular dynamics simulations of both basal surfaces with and without hydration waters reveal that gibbsite surface hydroxyls interact only weakly with overlying hydration waters remaining essentially unperturbed, whereasthose on boehmite can interact more strongly facilitated by higher configurational degrees of freedom at the interface. The findings clearly unveil substantial differences in the hydrated interfacial dynamics of these two otherwise similar materials, with implications for their interfacial chemistry and wettability.

Sassi, Michel JPC↗
DOE OSTI2020

The Role of Ligand–Ligand Interactions in Multimodal Ligand Conformational Equilibria and Surface Pattern Formation

Multimodal chromatography uses multiple modes of interaction such as charge, hydrophobic, or hydrogen bonding to separate proteins. Recently, we used molecular dynamics (MD) simulations to show that ligands immobilized on surfaces can interact and associate with neighboring ligands to form hydrophobic and charge patches, which may have important implications for the nature of protein–surface interactions. Here, we study interfacial systems of increasing complexity—from a single immobilized multimodal ligand to high density surfaces—to better understand how ligand behavior is affected by the presence of a surface and the presence of other ligands in the vicinity, and how this behavior scales to larger systems. Furthermore, we find that tethering a ligand to a surface restricts its conformations to a subset of those observed in free solution, yet the ligand maintains flexibility in the plane of the surface and can form contacts with neighboring ligands. We find that although the formation of a contact between two neighboring ligands is slightly unfavorable, three neighboring ligands exhibit a preference for the formation of a fully connected cluster. To explore how these trends in ligand association extend to a larger surface with high density of ligands, we performed coarse-grained Monte Carlo (MC) simulations of a 132-ligand surface using ligand interactions parametrized based on free energies obtained from the three-ligand MD simulations. Despite their simplicity, the coarse-grained simulations qualitatively capture the cluster size distribution of ligands observed in detailed MD simulations. Quantitative differences between the two suggest opportunities for improvements in the coarse-grained energy function for efficient predictions of cluster and pattern formations. Our approach presents a promising route to the engineering of multimodal patterns for future chromatographic resin design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Materials design of sodium chloride solid electrolytes Na3MCl6 for all-solid-state sodium-ion batteries

All-solid-state sodium-ion batteries have attracted increasing attention owing to the low cost of sodium and the enhanced safety compared to conventional Li-ion batteries. Recently, halides have been considered as promising solid electrolytes (SEs) due to their favorable combination of high ionic conductivity and chemical stability against high-voltage cathode materials. Although a wide variety of lithium chloride SEs, Li 3 MCl 6 , have been developed for high-voltage all-solid-state batteries, only a limited number of sodium chloride SEs have been reported. This study aims to offer a material design insight for the development of sodium chloride SEs through systematic assessment of the phase stability, electrochemical stability, and transport properties of novel Na 3 MCl 6 SEs. Structural calculations indicate that Na 3 MCl 6 exhibits trigonal $P\bar{3}$1c, monoclinic P2 1 /n, and trigonal $R\bar{3}$ phases, and the stable phase of Na 3 MCl 6 is dependent on the type and ionic radius of M. Na 3 MCl 6 typically exhibits a high oxidation potential, demonstrating good electrochemical stability against cathodes. The bond-valence site energy and ab initio molecular dynamics calculations revealed that Na 3 MCl 6 with P2 1 /n and $R\bar{3}$ phases showed low ionic conductivity, while the $P\bar{3}$1c phase slightly improved the ionic conductivity of Na 3 MCl 6 . The formation of Na vacancies by aliovalent substitution considerably increased the ionic conductivity up to four orders of magnitude for pristine Na 3 MCl 6 , exhibiting ~10 –5 S cm –1 for trigonal $P\bar{3}$1c and $R\bar{3}$ phases. The formation of defects could further enhance the ionic conductivity of Na 3 MCl 6 , and the optimization of defect type and ratio can be helpful in developing superionic Na chloride SEs. The material design of Na 3 MCl 6 in this study will provide fundamental guidelines for the development of novel sodium halide SEs for all-solid-state sodium-ion batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Active learning of neural network potentials for rare events

Developing an automated active learning framework for Neural Network Potentials, focusing on accurately simulating bond-breaking in hexane chains through steered molecular dynamics sampling and assessing model transferability.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2023

How an electrical current can stabilize a molecular nanojunction

Molecular junctions at the brink of their stability typically undergo structural changes that affect their conductance properties. This effect provides a feedback mechanism that can stabilize molecular junctions against current-induced bond-rupture.

Chemistry↗
DOE OSTI2023

Subsurface spectroscopy of heterogeneous materials using optical wavefront shaping

Plastic-bonded explosives and propellants consist of energetic molecular crystals embedded in a polymer matrix that also includes additives, such as taggants, plasticizers, grit, antioxidants, etc. Furthermore, this heterogeneous composition renders these materials optically opaque, limiting optical characterization techniques (e.g., Raman spectroscopy) to probing chemical reactions at the sur-face. However, many reactions of interest are believed to occur inside the material where current optical techniques can not probe. To address this challenge, we have developed a new optical technique that utilizes feedback assisted wavefront shaping (using spatial light modulators) to focus probe light inside a heterogeneous material, such that we can perform subsurface spectroscopy. Recently, we demonstrated this technique by monitoring subsurface photodegradation and thermal degradation of Eu-doped molecular crystals using both fluorescence and Raman spectroscopy. Based off these successes we are now looking into improvements to this technique to allow for greater time resolution, including replacing our spatial light modulators with fast digital mirror devices, using ns optical phase conjugation, and self-healing optical beams.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

An unexpected hydratase synthesizes the green light-absorbing pigment fucoxanthin

Abstract The ketocarotenoid fucoxanthin and its derivatives can absorb blue–green light enriched in marine environments. Fucoxanthin is widely adopted by phytoplankton species as a main light-harvesting pigment, in contrast to land plants that primarily employ chlorophylls. Despite its supreme abundance in the oceans, the last steps of fucoxanthin biosynthesis have remained elusive. Here, we identified the carotenoid isomerase-like protein CRTISO5 as the diatom fucoxanthin synthase that is related to the carotenoid cis–trans isomerase CRTISO from land plants but harbors unexpected enzymatic activity. A crtiso5 knockout mutant in the model diatom Phaeodactylum tricornutum completely lacked fucoxanthin and accumulated the acetylenic carotenoid phaneroxanthin. Recombinant CRTISO5 converted phaneroxanthin into fucoxanthin in vitro by hydrating its carbon–carbon triple bond, instead of functioning as an isomerase. Molecular docking and mutational analyses revealed residues essential for this activity. Furthermore, a photophysiological characterization of the crtiso5 mutant revealed a major structural and functional role of fucoxanthin in photosynthetic pigment–protein complexes of diatoms. As CRTISO5 hydrates an internal alkyne physiologically, the enzyme has unique potential for biocatalytic applications. The discovery of CRTISO5 illustrates how neofunctionalization leads to major diversification events in evolution of photosynthetic mechanisms and the prominent brown coloration of most marine photosynthetic eukaryotes.

Biochemistry & Molecular Biology↗
DOE OSTI2022

Boson Fermion Nucleus Correspondence With Second Period Primary Valencies And Bonding Angles: Monograph #15

The Boson Fermion Nuclei (BFN) in the second period of the periodic table of elements have structure. BFN nuclei of hydrogen and helium isotopes in the first period serve as building blocks for BFN in the second period. The building block nuclei in the first period have specific chemical bonding characteristics that carry over to their presence as building blocks in the BFN structures in the second period. The nuclear structure was created as a least energy nuclear configuration during stellar nucleosynthesis. The nuclear structure determines the principal valence and bonding angle of the second period element without consideration of Lewis structures, valence bond theory (VBT), orbital mixing and hybridization, molecular orbital theory (MOT), or valence shell electron pair repulsion (VSEPR) theory.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Bond clusters control rupture force limit in shear loaded histidine-Ni 2+ metal-coordinated proteins

Dynamic noncovalent interactions are pivotal to the structure and function of biological proteins and have been used in bioinspired materials for similar roles. Metal-coordination bonds, in particular, are especially tunable and enable control over static and dynamic properties when incorporated into synthetic materials. Despite growing efforts to engineer metal-coordination bonds to produce strong, tough, and self-healing materials, the systematic characterization of the exact contribution of these bonds towards mechanical strength and the effect of geometric arrangements is missing, limiting the full design potential of these bonds. In this work, we engineer the cooperative rupture of metal-coordination bonds to increase the rupture strength of metal-coordinated peptide dimers. Utilizing all-atom steered molecular dynamics simulations on idealized bidentate histidine-Ni 2+ coordinated peptides, we show that histidine-Ni 2+ bonds can rupture cooperatively in groups of two to three bonds. We find that there is a strength limit, where adding additional coordination bonds does not contribute to the additional increase in the protein rupture strength, likely due to the highly heterogeneous rupture behavior exhibited by the coordination bonds. Further, we show that this coordination bond limit is also found natural metal-coordinated biological proteins. Using these insights, we quantitatively suggest how other proteins can be rationally designed with dynamic noncovalent interactions to exhibit cooperative bond breaking behavior. Altogether, this work provides a quantitative analysis of the cooperativity and intrinsic strength limit for metal-coordination bonds with the aim of advancing clear guiding molecular principles for the mechanical design of metal-coordinated materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Adsorption-Engineered Hydrocarbon Ionomers for Durable Proton-Exchange Membrane Fuel Cells

Reducing reliance on perfluoroalkyl substances (PFAS) in proton-exchange membrane fuel cells requires hydrocarbon ionomers that combine high performance with long-term durability, a persistent challenge in catalyst-layer design. Here, we identify oxidation-driven ionomer-catalyst interfacial degradation as a dominant failure pathway in hydrocarbon ionomer-bonded cathodes and introduce an adsorption-engineering strategy to overcome this limitation. The comparison of a commercial sulfonated poly(phenylene) (Pemion) with structurally engineered sulfonated poly(fluorene)s demonstrated that electrode durability is governed by the interplay between ionomer adsorption strength and resistance to oxidative degradation on carbon-supported Pt catalysts. A poly(fluorene) ionomer with mobile alkyl sulfonic acid groups forms resilient interfaces, delivering 1.28 A cm−2 at 0.65 V under fully humidified H2/air conditions (80°C and 150 kPaabs), comparable to Pemion. After 90,000 accelerated potential cycles, the poly(fluorene)-bonded cathode exhibits significantly improved durability, with only 29% performance loss compared to 58% for Pemion; further molecular refinement reduces the loss to 17%, approaching that of Nafion-bonded cathodes (14%). These findings establish adsorption-engineered ionomer design that decouples interfacial anchoring from oxidative degradation as a general strategy for achieving durable, high-performance PFAS-free PEM fuel cell electrodes.

08 HYDROGEN↗
DOE OSTI2020

Th 2 O – , Th 2 Au – , and Th 2 AuO 1,2 – Anions: Photoelectron Spectroscopic and Computational Characterization of Energetics and Bonding

The observation and characterization of the anions: Th 2 O – , Th 2 Au – , and Th 2 AuO 1,2 – is reported. These species were studied through a synergetic combination of anion photoelectron spectroscopy and ab initio correlated molecular orbital theory calculations at the CCSD(T) level with large correlation-consistent basis sets. To better understand the energetics and bonding in these anions and their corresponding neutrals, a range of smaller diatomic to tetratomic species were studied computationally. Correlated molecular orbital theory calculations at the CCSD(T) level showed that in most of these cases, there are close-lying anions and neutral clusters with different geometries and spin states and are consistent with the experimentally observed spectra. Thus, comparison of experimentally determined and computationally predicted vertical detachment energies and electron affinities for different optimized geometries and spin states shows excellent agreement to within 0.1 eV. The structures for both the neutrals and anions have a significant ionic component to the bonding because of the large electron affinity of the Au atom and modest ionization potentials for Th 2 , Th 2 O, and Th 2 O 2 . The analysis of the bonding for the Th–Th bonds from the molecular orbitals is consistent with this ionic model. The results show that there is a wide variation in the bond distance from 2.7 to 3.5 Å for the Th–Th bonds all of which are less than twice the atomic radius of Th of 3.6 Å. The bond distances encompass bond orders from 4 to 0. Furthermore, there can be different bond orders for the same bond distance depending on the nature of the ionic bonding suggesting that one may not be able to correlate the bond order with the bond distance in these types of clusters. In addition, the presence of an Au atom may provide a unique probe of the bonding in such clusters because of its ability to accept an electron from clusters with modest ionization potentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Assessing Melting and Solid–Solid Transition Properties of Choline Chloride via Molecular Dynamics Simulations

Choline chloride (ChCl) is used extensively as a hydrogen bond donor in deep eutectic solvents (DESs). However, determining its melting properties experimentally is challenging due to decomposition upon melting, leading to widely varying literature values. Accurate melting properties are crucial for understanding the solid–liquid phase behavior of ChCl-containing DESs. Here, we employ molecular dynamics simulations to compute the phase transitions of ChCl, testing a variety of atomistic force fields. We find that the results are sensitive to the choice of force field, but a melting temperature of 627 K and a melting enthalpy of 7.8 kJ/mol seem most reasonable, in good agreement with some literature values. Furthermore, we suggest these as the likely melting properties of ChCl, though the results are tentative due to limited experimental data for the liquid ChCl phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Oxygen magnetic polarization, nodes in spin density, and zigzag spin order in oxides

Recent studies on Ba 2 CoO 4 (BCO) and SrRuO 3 (SRO) have unveiled a variety of intriguing phenomena, such as magnetic polarization on oxygens, unexpected nodes in the spin density profile along bonds, and unusual zigzag spin patterns in triangular lattices. Here, using simple model calculations supplemented by density functional theory we explain the presence of nodes based on the antibonding character of the dominant singly occupied molecular orbitals along the transition metal (TM) to oxygen bonds. Our simple model also allows us to explain the net polarization on oxygen as originated from the hybridization between atoms and mobility of the electrons with spins opposite to those of the closest TM atoms. Overall, our results are not limited to BCO and SRO, but they are generic and qualitatively predict the net polarization expected on any ligands, according to the spin order of the closest TM atoms and the number of intermediate ligand atoms. Finally, we propose that a robust easy-axis anisotropy would suppress the competing 120° antiferromagnetic order to stabilize the zigzag pattern order as ground state in a triangular lattice. Our generic predictions should be applicable to any other compound with characteristics similar to those of BCO and SRO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Electrostatic control of photoisomerization pathways in proteins

Rotation around a specific bond after photoexcitation is central to vision and emerging opportunities in optogenetics, super-resolution microscopy, and photoactive molecular devices. Competing roles for steric and electrostatic effects that govern bond-specific photoisomerization have been widely discussed, the latter originating from chromophore charge transfer upon excitation. We systematically altered the electrostatic properties of the green fluorescent protein chromophore in a photoswitchable variant, Dronpa2, using amber suppression to introduce electron-donating and electron-withdrawing groups to the phenolate ring. Through analysis of the absorption (color), fluorescence quantum yield, and energy barriers to ground- and excited-state isomerization, we evaluate the contributions of sterics and electrostatics quantitatively and demonstrate how electrostatic effects bias the pathway of chromophore photoisomerization, leading to a generalized framework to guide protein design.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Molecular structure retrieval directly from laboratory-frame photoelectron spectra in laser-induced electron diffraction

Ubiquitous to most molecular scattering methods is the challenge to retrieve bond distance and angle from the scattering signals since this requires convergence of pattern matching algorithms or fitting methods. This problem is typically exacerbated when imaging larger molecules or for dynamic systems with little a priori knowledge. Here, we employ laser-induced electron diffraction (LIED) which is a powerful means to determine the precise atomic configuration of an isolated gas-phase molecule with picometre spatial and attosecond temporal precision. We introduce a simple molecular retrieval method, which is based only on the identification of critical points in the oscillating molecular interference scattering signal that is extracted directly from the laboratory-frame photoelectron spectrum. The method is compared with a Fourier-based retrieval method, and we show that both methods correctly retrieve the asymmetrically stretched and bent field-dressed configuration of the asymmetric top molecule carbonyl sulfide (OCS), which is confirmed by our quantum-classical calculations.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Atomic Orbital Energy Matching vs Overlap in Actinide-Ligand Dative Bonding

Prebonding conditions and dative bond formation in actinide(IV)hexachloride complexes with U, Np, and Pu are studied by density functional theory (DFT) calculations, focusing on the interplay of atomic orbital (AO) overlap and AO energy matching in the formation of molecular orbitals (MOs) and the subsequent identification of dative bonds. The extent of donation is tracked via population analysis, MO localization, and bond-order criteria. DFT Fock matrices are used to setup models in which varying numbers of valence AOs interact to form dative bonds. The results confirm, among other effects, a contribution to metal−ligand covalency from the actinide (An) 6p shell. Better matching of An(5f) and Cl(3p) energies occurs as the An(5f) level stabilizes with increasing An effective nuclear charge. A near-degeneracy occurs in the case of the α-spin orbitals of the Pu system, but it is inconsequential. Altogether, better AO energy matching for An(5f) and Cl(3p) along the series U, Np, Pu is counter-balanced by decreasing AO overlap and decreasing availability of 5f acceptor orbitals, leading to similar bond orders and extents of donation in the three systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Foundational insights into the mechanical and molecular evolution of porcine skin gelatin during gelation

Gelatin is a widely used material in biomedical fields, particularly in regenerative medicine and tissue engineering, due to its biocompatibility and versatile properties. While prior research has explored methods to enhance gelatin's mechanical strength and stability, fundamental studies on gelatin, specifically its curing process, mechanical stiffness, and chemical evolution during gelation, remain limited. This study uses ultrasonic testing and Fourier Transform Infrared Spectroscopy (FTIR) to examine gelatin's stiffness and molecular changes during gelation. Samples of 175 and 300 Porcine Skin Bloom Strength Gelatin at concentrations of 2% and 6% (w/v) were analyzed. Through transmission ultrasonic testing helped identify key transition points in gelation, with higher concentrations exhibiting delayed transitions. FTIR revealed that C-N bond formation peaks early while N-H bond deformation persists. A correlation emerged between sound speed and peak absorbance, suggesting that changes in molecular mobility may contribute to the observed sound speed behavior during periods of active bond formation. However, as gelation continues, fewer bonding components may be available, potentially decreasing molecular movement and contributing to the observed increase in sound speed. These findings provide insights into gelatin's mechanical and chemical evolution, offering a framework for improved control over its gelation kinetics. Swept-Frequency Acoustic Interferometry (SFAI) was performed at the end of the curing process to measure the sound speed, enabling the calculation of the bulk moduli of the gelatin samples. The combined use of ultrasonic and FTIR testing provides a non-destructive method for characterizing gelatin and other biomaterials. This approach advances understanding of gelatin curing behavior and supports the development of safer biomaterials with tailored mechanical properties for various applications such as tissue engineering and regenerative medicine.

Biomaterials↗
DOE OSTI2022

A Molecular Description of Hydrogel Forming Polymers for Cement-Based Printing Paste Applications

This research endeavors to link the physical and chemical characteristics of select polymer hydrogels to differences in printability when used as printing aids in cement-based printing pastes. A variety of experimental probes including differential scanning calorimetry (DSC), NMR-diffusion ordered spectroscopy (DOSY), quasi-elastic neutron scattering (QENS) using neutron backscattering spectroscopy, and X-ray powder diffraction (XRD), along with molecular dynamic simulations, were used. Conjectures based on objective measures of printability and physical and chemical-molecular characteristics of the polymer gels are emerging that should help target printing aid selection and design, and mix formulation. Molecular simulations were shown to link higher hydrogen bond probability and larger radius of gyration to higher viscosity gels. Furthermore, the higher viscosity gels also produced higher elastic properties, as measured by neutron backscattering spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗