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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Effect of K + Force Fields on Ionic Conductivity and Charge Dynamics of KOH in Ethylene Glycol

Predicting ionic conductivity is crucial for developing efficient electrolytes for energy storage and conversion and other electrochemical applications. An accurate estimate of ionic conductivity requires understanding complex ion–ion and ion–solvent interactions governing the charge transport at the molecular level. Molecular simulations can provide key insights into the spatial and temporal behavior of electrolyte constituents. However, such insights depend on the ability of force fields to describe the underlying phenomena. In this work, molecular dynamics simulations were leveraged to delineate the impact of force field parameters on ionic conductivity predictions of potassium hydroxide (KOH) in ethylene glycol (EG). Four different force fields were used to represent the K + ion. Diffusion-based Nernst–Einstein and correlation-based Einstein approaches were implemented to estimate the ionic conductivity, and the predicted values were compared with experimental measurements. The physical aspects, including ion-aggregation, charge distribution, cluster correlation, and cluster dynamics, were also examined. A force field was identified that provides reasonably accurate Einstein conductivity values and a physically coherent representation of the electrolyte at the molecular level.

25 ENERGY STORAGE↗
NASA NTRS2005

GEMS Revealed: Spectrum Imaging of Aggregate Grains in Interplanetary Dust

Anhydrous interplanetary dust particles (IDPs) of cometary origin contain abundant materials that formed in the early solar nebula. These materials were transported outward and subsequently mixed with molecular cloud materials and presolar grains in the region where comets accreted [1]. GEMS (glass with embedded metal and sulfides) grains are a major component of these primitive anhydrous IDPs, along with crystalline Mg-rich silicates, Fe-Ni sulfides, carbonaceous material, and other trace phases. Some GEMS grains (~5%) are demonstrably presolar based on their oxygen isotopic compositions [2]. However, most GEMS grains are isotopically solar and have bulk chemical compositions that are incompatible with inferred compositions of interstellar dust, suggesting a solar system origin [3]. An alternative hypothesis is that GEMS grains represent highly irradiated interstellar grains whose oxygen isotopic compositions were homogenized through processing in the interstellar medium (ISM) [4]. We have obtained the first quantitative X-ray maps (spectrum images) showing the distribution of major and minor elements in individual GEMS grains. Nanometer-scale chemical maps provide critical data required to evaluate the differing models regarding the origin of GEMS grains.

Keller, L. P.↗
DOE OSTI2020

Probing Self-Assembly in Arginine–Oleic Acid Solutions with Terahertz Spectroscopy and X-ray Scattering

A study of the formation of microstructures in the reaction of oleic acid with arginine elucidates dynamical self-assembly processes at the molecular level. Terahertz spectroscopy combined with density functional calculations reveals the initial hydrogen-bonding motifs in the assembly process, leading to the formation of micelles and vesicles. Small-angle X-ray scattering measurements allow for kinetic analysis of the growth processes of these nanostructures, revealing a prenucleation pathway of vesicles and micelles which lead to spongelike structures. This final stage of the assembly into spongelike aggregates is investigated with optical microscopy. The formed structures only occur at pH > 8 and are resistant to extreme acidic and basic conditions. Here, a mechanistic pathway to the formation of the spongelike aggregates is described.

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

Aqueous Self‐Assembly of Cylindrical and Tapered Bottlebrush Block Copolymers

The self‐assembly of amphiphilic bottlebrush block copolymers (BCPs), featuring backbones densely grafted with two types of side chains, is less well understood compared to linear BCPs. In particular, the solution self‐assembly of tapered bottlebrush BCPs—cone‐shaped BCPs with hydrophilic or hydrophobic tips—remains unexplored. This study investigates eight tapered and four cylindrical bottlebrush BCPs with varied ratios of hydrophobic polystyrene (PS) and hydrophilic poly(acrylic acid) (PAA) side chains, synthesized via sequential addition of macromonomers using ring‐opening metathesis polymerization (SAM‐ROMP). Self‐assembled nanostructures formed in water were analyzed using cryogenic transmission electron microscopy, small‐angle neutron scattering, and dynamic light scattering. Most BCPs generated multiple nanostructures with surface protrusions, including spherical micelles, cylindrical micelles, and vesicles, alongside transitional forms like ellipsoids and semi‐vesicles. Coarse‐grained molecular dynamics simulations supported the experimental findings, which revealed two distinct self‐assembly pathways. The first involved micelle fusion, producing elliptical and cylindrical aggregates, sometimes forming Y‐junctions. The second pathway featured micelle maturation into semivesicles, which developed into vesicles or large compound vesicles. This work provides the first experimental evidence of vesicle formation via semivesicles in bottlebrush BCPs and demonstrates the significant influence of cone directionality on self‐assembly behavior in these cone‐shaped polymeric amphiphiles.

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

Ion Pairing, Clustering and Transport in a LiFSI-TMP Electrolyte as Functions of Salt Concentration using Molecular Dynamics Simulations

Battery capacity is highly related to ion-pairing mechanisms in electrolytes, since a cluster formation can lead to dead Li formation, reducing the number of charge carriers and leading to capacity fading. We use molecular dynamics simulations to model an electrolyte comprising trimethyl phosphate (TMP) solvent and a lithium bis(fluorosulfonyl)imide (LiFSI) salt, exploring effects of salt concentration on solvation and ion-transport. We simulate the LiFSI-TMP electrolyte for salt concentrations of 0.7, 1.43 and 3.82 molar. A statistical analysis was performed to study ion-pairing, clustering, diffusivity, conductivity, and coordination of Li-ions, providing insights into relations between molecular structures and transport properties. Molecular structure of ionic components changes as concentration increases, from a predominant solvent separated ion pair (SSIP) and contact ion pair (CIP) to aggregate salt (AGG) and ionic cluster formation. Given the formation of the ionic cluster, the diffusion mechanism followed by Li-ions changes from a hopping/exchange to a vehicular mechanism as concentration increases; this is reflected in a decrease of ionic conductivities. Ionicity was also calculated to reveal how the ionic motion changes from an uncorrelated to a correlated one as the salt concentration increases. Furthermore, we also compared our results with experimental calculations performed for similar electrolyte systems

25 ENERGY STORAGE↗
DOE OSTI2021

Polyethylene Glycol Crowder’s Effect on Enzyme Aggregation, Thermal Stability, and Residual Catalytic Activity

Protein stability and performance in various natural and artificial systems incorporating many other macromolecules for therapeutic, diagnostic, sensor, and biotechnological applications attract increasing interest with the expansion of these technologies. Here we address the catalytic activity of lysozyme protein (LYZ) in the presence of a polyethylene glycol (PEG) crowder in a broad range of concentrations and temperatures in aqueous solutions of two different molecular mass PEG samples (Mw = 3350 and 10000 g/mol). The phase behavior of PEG–protein solutions is examined by using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS), while the enzyme denaturing is monitored by using an activity assay (AS) and circular dichroism (CD) spectroscopy. Molecular dynamic (MD) simulations are used to illustrate the effect of PEG concentration on protein stability at high temperatures. The results demonstrate that LYZ residual activity after 1 h incubation at 80 °C is improved from 15% up to 55% with the addition of PEG. The improvement is attributed to two underlying mechanisms. (i) Primarily, the stabilizing effect is due to the suppression of the enzyme aggregation because of the stronger PEG–protein interactions caused by the increased hydrophobicity of PEG and lysozyme at elevated temperatures. (ii) The MD simulations showed that the addition of PEG to some degree stabilizes the secondary structures of the enzyme by delaying unfolding at elevated temperatures. The more pronounced effect is observed with an increase in PEG concentration. This trend is consistent with CD and AS experimental results, where the thermal stability is strengthened with increasing of PEG concentration and molecular mass. Overall, the results show that the highest stabilizing effect is approached at the critical overlap concentration of PEG.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Chain conformations and phase separation in polymer solutions with varying solvent quality

Molecular dynamics simulations are used to investigate the conformations of a single polymer chain, represented by the Kremer-Grest bead-spring model, in a solution with a Lennard-Jones liquid as the solvent when the interaction strength between the polymer and solvent is varied. Results show that when the polymer-solvent interaction is unfavorable, the chain collapses as one would expect in a poor solvent. For more attractive polymer-solvent interactions, the solvent quality improves and the chain is increasingly solvated and exhibits ideal and then swollen conformations. However, as the polymer-solvent interaction strength is increased further to be more than about twice the strength of the polymer-polymer and solvent-solvent interactions, the chain exhibits an unexpected collapsing behavior. Correspondingly, for strong polymer-solvent attractions, phase separation is observed in the solutions of multiple chains. These results indicate that the solvent becomes effectively poor again at very attractive polymer-solvent interactions. Nonetheless, the mechanism of chain collapsing and phase separation in this limit differs from the case with a poor solvent rendered by unfavorable polymer-solvent interactions. In the latter, the solvent is excluded from the domain of the collapsed chains while in the former, the solvent is still present in the pervaded volume of a collapsed chain or in the polymer-rich domain that phase separates from the pure solvent. Finally, in the limit of strong polymer-solvent attractions, the solvent behaves as a glue to stick monomers together, causing a single chain to collapse and multiple chains to aggregate and phase separate.

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

Impact of fluorination on Li + solvation and dynamics in ionic liquid-hydrofluoroether locally concentrated electrolytes

The thermal, physical, structural, and transport properties of ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide [PYR14][TFSI] and Li-salts of lithium (nonafluorobutane)(trifluoromethanesulfonyl)imide [Li][IM14] and [Li][TFSI] (0 ≤ x Li ≤ 0.3), with addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) (0 ≤ x TTE ≤ 0.45) were studied. While [IM14] increases glass transition, TTE improves conductivity over a wider liquidus range. Li + is solvated primarily by [TFSI] with some contribution by [IM14]. However, both 7 Li- 19 F HOESY NMR and spatial distribution functions (SDFs) derived from molecular dynamics (MD) indicate short contacts between the fluorines of TTE and Li + . This is a result of tighter anion-solvated Li + without aggregation of the Li + solvates, consistent with Raman measurements, thus confirming the existence of fluorous domains in the bulk which leads to improved fluidity and a Li + diffusivity of 1.26 x 10 –12 m 2 /s at 0 °C (x Li = 0.20) with a Li + transference of 0.16. Improved transport properties translated to a higher capacity of the TTE/IL electrolyte in a Li||LiFePO 4 half-cell with 95mAh/g at 0.1C, compared to the IL electrolyte without TTE (60 mAh/g). Furthermore, this study demonstrates the tunability of solvation and transport properties in IL electrolytes by asymmetric fluorinated anions and hydrofluoroether co-solvents for low temperature Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Habitat Affinity of Riverine Dissolved Organic Matter Linked to Molecular Traits

Fluxes of organic matter across Earth habitats shape ecosystem function and carbon storage. Yet, it is challenging to predict howthe molecules are preferentially accumulated in specific habitats, that is, the habitat affinities, due to their diverse character-istics. Here, we develop an indicator of compositional-level habitat affinity for dissolved organic matter (DOM) by quantifyingthe aggregated affinities of individual molecules that are over- or under-represented relative to a reference habitat. Applyingthis indicator to 93 paired riverine water-sediment sites, we find that 65.1% of molecules show non-significant habitat affinitiesfor water or sediment and are thermodynamically favorable and susceptible to microbial degradation. Consistently, the habitataffinities of DOM assemblages decrease with lower molecular weights and recalcitrance for waters, and with higher thermody-namic favorability for sediments. These affinities are both reduced by elevated temperatures and anthropogenic pressures, suchas nitrogen loading and land-use change. Our projection of habitat affinities of global riverine DOM shows that regions withintense anthropogenic disturbances or warm climates, such as East Asia, Western Europe, and the Amazon, tend to exhibit loweraffinities. These findings suggest enhanced molecular homogenization between water and sediment habitats is associated withenvironmental changes and underscore the importance of habitat affinities for predicting the potential trajectories of organiccarbon across ecosystems

Cui, Yifan↗
DOE OSTI2021

Tuning Conjugated Polymer Chain Packing for Stretchable Semiconductors

We report in order to apply polymer semiconductors to stretchable electronics, they need to be easily deformed under strain without being damaged. A small number of conjugated polymers, typically with semicrystalline packing structures, have been reported to exhibit mechanical stretchability. Herein, a method is reported to modify polymer semiconductor packing-structure using a molecular additive, dioctyl phthalate (DOP), which is found to act as a molecular spacer, to be inserted between the amorphous chain networks and disrupt the crystalline packing. As a result, large-crystal growth is suppressed while short-range aggregations of conjugated polymers are promoted, which leads to an improved mechanical stretchability without affecting charge-carrier transport. Due to the reduced conjugated polymer intermolecular interactions, strain-induced chain alignment and crystallization are observed. By adding DOP to a well-known conjugated polymer, poly[2,5-bis(4-decyltetradecyl)pyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione-(E)-1,2-di(2,2 '-bithiophen-5-yl)ethene] (DPPTVT), stretchable transistors are obtained with anisotropic charge-carrier mobilities under strain, and stable current output under strain up to 100%.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Correlated Ion Transport Governed by Dynamic Local Structure in High Concentration and Localized High Concentration Electrolytes

Understanding the dynamics of cluster formation and network percolation provides the mechanistic link between microscopic solvation structure and transport in concentrated electrolytes, including localized high-concentration electrolytes (LHCEs). Although recent studies have shown LHCEs to form micelle-like aggregates at specific compositions, a quantitative understanding of how solvation structures and transport properties depend on salt–solvent–diluent ratios remains limited. Here, we integrate molecular dynamics with Onsager transport analyses to chart the evolution of solvation microstructure and associated ionic transport in LiFSI/DMC/TTE, achieving good agreement with experimental conductivities across composition. We show that micelle formation arises from a dynamic instability of the cation–anion network, and that network percolation is the primary determinant of conductivity. Two compositional thresholds emerge: A critical network concentration (CNC) and a critical micelle concentration (CMC) that delineate transitions from extended percolating networks to micelle-like clusters and then to fragments. These structural transitions rationalize the nonintuitive conductivity decrease at intermediate dilution despite monotonically decreasing viscosity and provide composition-level design rules for LHCEs.

Mohanakrishnan, Rohith Srinivaas [University of Ca↗
NASA NTRS2017

Organics and Ices in the Outer Solar System: Connections to the Interstellar Medium

The solar nebula, that aggregate of gas and dust that formed the birthplace of the Sun, planets and plethora of small bodies comprising the Solar System, originated in a molecular cloud that is thought to have spawned numerous additional stars, some with their own planets and attendant small bodies. The question of the chemical and physical reprocessing of the original interstellar materials in the solar nebula has challenged both theory and observations. The acquisition and analysis of samples of comet and asteroid solids, and a growing suite of in-situ and close-up analyses of relatively unaltered small Solar System bodies now adds critical new dimensions to the study of the origin and evolution of the early solar nebula. Better understanding the original composition of the material from which our solar nebula formed, and the processing that material experienced, will aid in formulations of chemistry that might occur in other solar systems. While we seek to understand the compositional history of planetary bodies in our own Solar System, we will inevitably learn more about the materials that comprise exoplanets and their surrounding systems.

SOLAR NEBULA↗
DOE OSTI2022

Effects of Salt Aggregation in Perfluoroether Electrolytes

Electrolytes comprised of polymers mixed with salts have great potential for enabling the use of Li metal anodes in batteries for increased safety. Ionic conductivity is one of the key performance metrics of these polymer electrolytes and achieving high room-temperature conductivity remains a challenge to date. For a bottom-up design of the polymer electrolytes, we must first understand how the structure of polyelectrolytes on a molecular level determines their properties. Here, we use classical molecular dynamics to study the solvation structure and ion diffusion in electrolytes composed of a short-chain perfluoroether with LiFSI or LiTFSI salts. Density functional theory is also used to provide some insights into the structures and energies of the salt interactions with the perfluoroether. We observe the formation of aggregates of salts in the fluorinated systems even at low salt concentrations. The fluorine-fluorine attraction in the solvent is the governing factor for creating the salt aggregates. The aggregates’ size and lifetime change with concentration and anion. These simulations provide an insight into the structure and dynamics of perfluoroether based electrolytes that can be used to improve Li-ion batteries.

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

Near‐Unity Superradiant Emission from Delocalized Frenkel Excitons in a Two‐Dimensional Supramolecular Assembly

Abstract Three general effective strategies are shown to mitigate nonradiative losses in the superradiant emission from supramolecular assemblies. J‐aggregates of 5,5′,6,6′‐tetrachloro‐1,1′‐diethyl‐3,3′‐di(4–sulfobutyl)‐benzimidazolocarbocyanine (TDBC) are used to elucidate the nature of nonradiative processes. Self‐annealing at room temperature (RT), photo‐brightening, and purification of the dye monomers are shown to all lead to substantial increases in emission quantum yields (QYs) and a concomitant lengthening of the emission lifetime, with purification having the largest effect. Structural and optical measurements are used to support a microscopic model that emphasizes the deleterious effects of a small number of impurity and defect sites that serve as nonradiative recombination centers. This understanding has yielded a molecular fluorophore in solution at RT with an unprecedented combination of fast emissive lifetime and high QY. Superradiant emission with a QY of 82% and a lifetime of 174 ps is obtained from J‐aggregates of TDBC in solution at RT. This combination of high QY and fast lifetime at RT makes supramolecular assemblies of purified TDBC a model system for the study of fundamental superradiance phenomena. High QY J‐aggregates are uniquely suited for the development of applications that require high speed and high brightness fluorophores such as devices for high‐speed optical communication.

36 MATERIALS SCIENCE↗
NASA NTRS1998

Determining the Molecular Growth Mechanisms of Protein Crystal faces by Atomic Force Microscopy

A high resolution atomic force microscopy (AFM) study had shown that the molecular packing on the tetragonal lysozyme (110) face corresponded to only one of two possible packing arrangements, suggesting that growth layers on this face were of bimolecular height (Li et al., 1998). Theoretical analyses of the packing had also indicated that growth of this face should proceed by the addition of growth units of at least tetramer size corresponding to the 43 helices in the crystal. In this study an AFM linescan technique was devised to measure the dimensions of individual growth units on protein crystal faces. The growth process of tetragonal lysozyme crystals was slowed down by employing very low supersaturations. As a result images of individual growth events on the (110) face were observed, shown by jump discontinuities in the growth step in the linescan images. The growth unit dimension in the scanned direction was obtained by suitably averaging these images. A large number of scans in two directions on the (110) face were performed and the distribution of lysozyme aggregate sizes were obtained. A variety of growth units, all of which were 43 helical lysozyme aggregates, were shown to participate in the growth process with a 43 tetramer being the minimum observed size. This technique represents a new application for AFM allowing time resolved studies of molecular process to be carried out.

Li, Huayu↗
DOE OSTI2023

Colloidal Clusters and Networks Formed by Oppositely Charged Nanoparticles with Varying Stiffnesses

Colloidal clusters and gels are ubiquitous in science and technology. Particle softness has a strong effect on interparticle interactions; however, our understanding of the role of this factor in the formation of colloidal clusters and gels is only beginning to evolve. Here, we report the results of experimental and simulation studies of the impact of particle softness on the assembly of clusters and networks from mixtures of oppositely charged polymer nanoparticles (NPs). Experiments were performed below or above the polymer glass transition temperature, at which the interaction potential and adhesive forces between the NPs were significantly varied. Hard NPs assembled in fractal clusters that subsequently organized in a kinetically arrested colloidal gel, while soft NPs formed dense precipitating aggregates, due to the NP deformation and the decreased interparticle distance. Importantly, interactions of hard and soft NPs led to the formation of discrete precipitating NP aggregates at a relatively low volume fraction of soft NPs. A phenomenological model was developed for interactions of oppositely charged NPs with varying softnesses. Furthermore, the experimental results were in agreement with molecular dynamics simulations based on the model. This work provides insight on interparticle interactions before, during, and after the formation of hard–hard, hard–soft, and soft–soft contacts and has impact for numerous applications of reversible colloidal gels, including their use as inks for additive manufacturing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

High-Pressure and Temperature Effects on the Clustering Ability of Monohydroxy Alcohols

This study examined the clustering behavior of monohydroxy alcohols, where hydrogen-bonded clusters of up to a hundred molecules on the nanoscale can form. By performing X-ray diffraction experiments at different temperatures and under high pressure, we investigated how these conditions affect the ability of alcohols to form clusters. The pioneering high-pressure experiment performed on liquid alcohols contributes to the emerging knowledge in this field. Implementation of molecular dynamics simulations yielded excellent agreement with the experimental results, enabling the analysis of theoretical models. Here we show that at the same global density achieved either by alteration of pressure or temperature, the local aggregation of molecules at the nanoscale may significantly differ. Surprisingly, high pressure not only promotes the formation of hydrogen-bonded clusters but also induces the serious reorganization of molecules. This research represents a milestone in understanding association under extreme thermodynamic conditions in other hydrogen bonding systems such as water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗