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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Modulation of Uptake and Reactivity of Nitrogen Dioxide in Metal-Organic Framework Materials

We report the modulation of reactivity of nitrogen dioxide (NO 2 ) in a charged metal–organic framework (MOF) material, MFM-305-CH 3 in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl - ions in the pores. Uptake of NO 2 into MFM-305-CH 3 leads to reaction between NO 2 and Cl - to give nitrosyl chloride (NOCl) and NO 3 - anions. A high dynamic uptake of 6.58 mmol g -1 at 298 K is observed for MFM-305-CH 3 as measured using a flow of 500 ppm NO 2 in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g -1 . The binding domains and reactivity of adsorbed NO 2 molecules within MFM-305-CH 3 and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.

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

Molecular Dynamics Simulation Study of the Protonation State Dependence of Glutamic Acid Transport through a Cyclic Peptide Nanotube

The effect of the protonation state of glutamic acid on its translocation through cyclic peptide nanotubes (CPNs) was assessed by using molecular dynamics (MD) simulations. Anionic (GLU–), neutral zwitterionic (GLU0), and cationic (GLU+) forms of glutamic acid were selected as three different protonation states for an analysis of energetics and diffusivity for acid transport across a cyclic decapeptide nanotube. Based on the solubility-diffusion model, permeability coefficients for the three protonation states of the acid were calculated and compared with experimental results for CPN-mediated glutamate transport through CPNs. Potential of mean force (PMF) calculations reveal that, due to the cation-selective nature of the lumen of CPNs, GLU–, so-called glutamate, shows significantly high free energy barriers, while GLU+ displays deep energy wells and GLU0 has mild free energy barriers and wells inside the CPN. The considerable energy barriers for GLU– inside CPNs are mainly attributed to unfavorable interactions with DMPC bilayers and CPNs and are reduced by favorable interactions with channel water molecules through attractive electrostatic interactions and hydrogen bonding. Unlike the distinct PMF curves, position-dependent diffusion coefficient profiles exhibit comparable frictional behaviors regardless of the charge status of three protonation states due to similar confined environments imposed by the lumen of the CPN. The calculated permeability coefficients for the three protonation states clearly demonstrate that glutamic acid has a strong protonation state dependence for its transport through CPNs, as determined by the energetics rather than the diffusivity of the protonation state. In addition, the permeability coefficients also imply that GLU– is unlikely to pass through a CPN due to the high energy barriers inside the CPN, which is in disagreement with experimental measurements, where a considerable amount of glutamate permeating through the CPN was detected. To resolve the discrepancy between this work and the experimental observations, several possibilities are proposed, including a large concentration gradient of glutamate between the inside and outside of lipid vesicles and bilayers in the experiments, the glutamate activity difference between our MD simulations and experiments, an overestimation of energy barriers due to the artifacts imposed in MD simulations, and/or finally a transformation of the protonation state from GLU– to GLU0 to reduce the energy barriers. Altogether, our study demonstrates that the protonation state of glutamic acid has a strong effect on the transport of the acid and suggests a possible protonation state change for glutamate permeating through CPNs.

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

Thermal Polymorphism in CsCB11H12

Thermal polymorphism in the alkali-metal salts incorporating the icosohedral monocarba-hydridoborate anion, CB11H12−, results in intriguing dynamical properties leading to superionic conductivity for the lightest alkali-metal analogues, LiCB11H12 and NaCB11H12. As such, these two have been the focus of most recent CB11H12− related studies, with less attention paid to the heavier alkali-metal salts, such as CsCB11H12. Nonetheless, it is of fundamental importance to compare the nature of the structural arrangements and interactions across the entire alkali-metal series. Thermal polymorphism in CsCB11H12 was investigated using a combination of techniques: X-ray powder diffraction; differential scanning calorimetry; Raman, infrared, and neutron spectroscopies; and ab initio calculations. The unexpected temperature-dependent structural behavior of anhydrous CsCB11H12 can be potentially justified assuming the existence of two polymorphs with similar free energies at room temperature: (i) a previously reported, ordered R3 polymorph stabilized upon drying and transforming first to R3c symmetry near 313 K and then to a similarly packed but disordered I43d polymorph near 353 K and (ii) a disordered Fm3 polymorph that initially appears from the disordered I43d polymorph near 513 K along with another disordered high-temperature P63mc polymorph. Quasielastic neutron scattering results indicate that the CB11H12− anions in the disordered phase at 560 K are undergoing isotropic rotational diffusion, with a jump correlation frequency [1.19(9) × 1011 s−1] in line with those for the lighter-metal analogues.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Polymer Architecture-Induced Trade-off between Conductivities and Transference Numbers in Salt-Doped Polymeric Ionic Liquids

Recent experiments have demonstrated that polymeric ionic liquids that share the same cation and anion but possess different architectures can exhibit markedly different conductivity and transference number characteristics when doped with lithium salt. In this study, we used atomistic molecular simulations on polymer chemistries inspired by the experiments to probe the mechanistic origins underlying the competition between conductivity and transference numbers. Our results indicate that the architecture of the polycationic ionic liquid plays a subtle but crucial role in modulating the anion–cation interactions, especially their dynamical coordination characteristics. Chemistries leading to longer-lived anion–cation coordinations relative to lithium–anion coordinations lead to lower conductivities and higher transference numbers. Furthermore, our results suggest that higher conductivities are accompanied by lower transference numbers and vice versa, revealing that alternative approaches may need to be considered to break this trade-off in salt-doped polyILs.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2022

Simulation of the photodetachment spectra of the nitrate anion (NO 3 ₋ ) in the B ~ 2 E' energy range and non-adiabatic electronic population dynamics of NO 3

The photodetachment spectrum of the nitrate anion (NO 3 ₋ ) in the energy range of the NO 3 second excited state is simulated from first principles using quantum wave packet dynamics. The prediction at 10 K and 435 K relies on the use of an accurate full-dimensional fully coupled five state diabatic potential model utilizing an artificial neural network. The ability of this model to reproduce experimental spectra was demonstrated recently for the lower energy range. Analysis of the spectra indicates a weaker Jahn–Teller coupling compared to the first excited state. The detailed non-adiabatic dynamics is studied by computing the population dynamics. An ultra-fast non-statistical radiationless decay is found only among the Jahn–Teller components, which is followed by a slow statistical non-radiative decay among the different state manifolds. The latter is reproduced perfectly by a simple first order kinetics model. The dynamics in the second excited state is not affected by the presence of a conical intersection with the first excited state manifold.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Molecular Origin of Nanoscale Anion Ordering of LiTFSI Electrolytes Revealed through SAXS/WAXS and Molecular Dynamics Simulations

Recent developments in “water-in-salt” electrolytes have precipitated a renewed effort to study imide-based electrolytes. While previous small-/wide-angle X-ray scattering (SAXS/WAXS) studies have attributed the emergence of a low-Q peak in the SAXS profile of aqueous LiTFSI electrolytes to nanometer-scale anion clustering, a molecular-level understanding of the root of these clusters remains unclear. Here, in this study, we combined molecular dynamics simulations and SAXS/WAXS to study the solvation structures of LiTFSI in acetonitrile, methanol, and water. We concluded that hydrogen bonding in water and MeOH stabilizes anion clusters, while nonpolar methyl groups on methanol and acetonitrile interrupt the nanoscale ordering of TFSI anions. This causes LiTFSI in water and MeOH electrolytes to exhibit two low-Q SAXS profile peaks while LiTFSI in acetonitrile exhibits only a single peak below Q = 1 Å –1 . These findings shed light on the underlying molecular origins of nanoscale anion clusters, which may help in the design of the next generation of electrolyte chemistries.

Trojanowski, Lucas [Univ. of Michigan, Ann Arbor, ↗
DOE OSTI2025

Unraveling the solvation phenomena of Ln 3+ cations in room-temperature ionic liquids: A computational study

Rare-earth elements (REEs), classified as critical materials, are difficult to separate due to their similar chemical properties and slight differences in ionic radius. Room-temperature ionic liquids (RTILs) have gained significant attention for REE separation because of their unique physicochemical properties and environmental advantages. In this study, we have investigated the solvation mechanisms of two RE cations (Ln 3+ ), Nd 3+ (light REE) and Yb 3+ (heavy REE), in two 1-butyl-3-methylimidazolium ([BMIM] + )-based RTILs using bis(trifluoromethylsulfonyl)imide ([NTf 2 ] − ) and acetate ([OAc] − ) as the respective anions, employing classical molecular dynamics (MD) simulations and density functional theory (DFT) techniques. From MD simulations, it is evident that Ln 3+ cations are primarily solvated by RTIL anions in the first solvation shell, while [BMIM] + cations form the second solvation shell with their numbers depending on the size and composition of the first solvation shell. The neutralizing [NO 3 − ] counterions are mainly solvated by [BMIM] + cations in their first solvation shell. Relative free energy change of solvation calculations using thermodynamic integration (TI) method indicate that Yb 3+ is more strongly solvated than Nd 3+ in both RTILs, a trend further supported by DFT calculations. While both methods predict consistent qualitative behavior, differences in models and energy evaluations lead to variations in absolute values. Overall, this study provides a comprehensive understanding of the solvation behavior of Ln 3+ cations in RTILs, demonstrating a stronger solvation preference for the heavy Ln 3+ cation (Yb 3+ ). In conclusion, these findings have implications for the design of RTIL-based separation processes for REEs.

Ash, Tamalika [Ames Lab., and Iowa State Univ., Am↗
DOE OSTI2025

Investigating Morphology and Diffusion in Simulations of Precise Anion-Conducting Polymers

Using atomistic molecular dynamics simulations, we investigate the morphology and transport properties of a new class of polymers which are functionalized with quaternary ammonium groups for use as anion exchange membranes. The polymers are precision polyolefins with either a trimethylammonium (p5CNMe3) or a dimethyl-hexyl ammonium (p5CNMe2Hx) pendant group at every fifth carbon along a polyethylene backbone. Simulations are performed at hydration levels of 5, 10, 15, and 20 water molecules per ammonium group. The hydrated polymers form nanoscale, percolated hydrophilic domains (water channels) in the hydrophobic polymer matrix that become wider with increasing water content. Water and hydroxide anion diffusion coefficients also increase with increasing water content. The morphology of the water domains is similar in both polymers, while the diffusion coefficients are somewhat lower in p5CNMe2Hx at fixed water content. Furthermore, the diffusion coefficients in both polymers fall on the same curve as a function of the fractal dimension of the percolated water channels, which appears to be a useful scalar measure of the effects of the nanoscale morphology on water and hydroxide anion transport.

Anion exchange membrane↗
DOE OSTI2022

Dynamic stability of a crude oil/brine interface: Effect of anion type

The chemical composition of the aqueous phase plays an essential role in water-based enhanced-oil recovery processes. The aqueous phase ionic profile affects the snap-off response of a crude oil-brine system by linking it to the brine-crude oil interfacial rheology. In this work, we focus on the effect of the anion on the snap-off response. To this end, a sample of crude oil from the Minnelusa Sandstone formation in Wyoming was selected, and several aqueous solutions were prepared with salts containing sodium cation and different anions (chlorides, sulfates, and phosphates) at two ionic strength values, 0.6 M and 6 mM, as cases of high- and low-salinity water. Interfacial tension, interfacial viscoelasticity and interface stability were analyzed as functions of aging time using pendant drop, dilatational rheology, and liquid bridge techniques, respectively. Here the results show that solutions with higher ionic strength led to the formation of more rigid interfaces, i.e. higher elastic modulus, and faster formation kinetics. In the low-salinity regime, solutions with polyvalent anions produce more viscoelastic interfaces at faster rates than solutions with monovalent anions. Finally, an excellent correlation (R 2 greater than 0.97) between the relative stability of the interfacial film, predicted in liquid bridge tests, and the ratio of interfacial tension and interfacial elastic modulus was found.

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

Silicon nanocluster anion-argon cation recombination via hybrid continuum-molecular dynamics calculations

Prediction of the charge distribution on particles in an aerosol is critical not only in electrical mobility based characterization methods, but also in understanding the role that charging plays in particle growth in gas phase synthesis reactors. The latter is particularly important in non-thermal plasma synthesis reactors, wherein nanoclusters form and grow from vapor phase precursors in a high electron and high ion density environment. In plasmas, because free electrons are much less massive and much more mobile than positive gas ions, nanocluster charge distributions are biased negative. Furthermore, neutral or even positively charged nanoclusters may exist, depending on the rate of nanocluster-gas ion recombination, and nanocluster-nanocluster collisions may greatly contribute to nanocluster growth if not Coulombically suppressed.

42 ENGINEERING↗
DOE OSTI2024

Site Disorder Drives Cyanide Dynamics and Fast Ion Transport in Li 6 PS 5 CN

Halide argyrodite solid-state electrolytes of the general formula Li 6 PS 5 X exhibit complex static and dynamic disorder that plays a crucial role in ion transport processes. Here, we unravel the rich interplay between site disorder and dynamics in the plastic crystal argyrodite Li 6 PS 5 CN and the impact on ion diffusion processes through a suite of experimental and computational methodologies, including temperature-dependent synchrotron powder X-ray diffraction, AC electrochemical impedance spectroscopy, 7 Li solid-state NMR, and machine learning-assisted molecular dynamics simulations. Sulfide and (pseudo)halide site disorder between the two anion sublattices unilaterally improves long-range lithium diffusion irrespective of the (pseudo)halide identity, which demonstrates the importance of site disorder in dictating bulk ionic conductivity in the argyrodite family. Furthermore, we find that anion site disorder modulates the presence and time scales of cyanide rotational dynamics. Ordered configurations of anions enable fast, quasi-free rotations of cyanides that occur on time scales of 10 11 Hz at T = 300 K. In contrast, we find that cyanide dynamics are slow or frozen in Li 6 PS 5 CN when site disorder between the cyanide and sulfide sublattices is present at T = 300 K. We rationalize the observed differences in cyanide dynamics in the context of elastic dipole interactions between neighboring cyanide anions and local strain induced by the configurations of site disorder that may impact the energetic landscape for cyanide rotational dynamics. Through this study, we find that anion disorder plays a decisive role in dictating the extent and time scales of both lithium ion and cyanide dynamics in Li 6 PS 5 CN.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Complex Dynamics in Argyrodite Solid-State Ion Conductors

Argyrodites are a compositionally diverse family of materials that exhibit remarkable ion transport properties. While the average crystal structures of argyrodites have been extensively studied, ion transport in these materials is governed by a confluence of dynamic processes spanning the cation, anion, and polyanionic sublattices. This Perspective synthesizes recent advances in understanding the role of dynamics in structural behavior and ion transport properties. We examine the compositional and structural motifs that govern order−disorder transitions within the argyrodite family and further explore how ion hopping is facilitated by lattice dynamics, from long-range phonons to local rotational dynamics of polyanionic species. Through the lens of dynamics spanning multiple time and length scales, we establish guiding principles that govern transport phenomena and highlight avenues of future study for the argyrodite family of ion conductors.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Expanded View of NMR Spin–Lattice Relaxation in Fluorine-Containing Ionic Liquids

Fluorine-containing anions are widely used in ionic liquids due to their unique physicochemical properties. However, the local dynamics of both cations and anions and their associated relaxation mechanisms remain incompletely understood. Here, we present a 1 H and 19 F spin–lattice relaxation rate (R1) study as a function of frequency over a broad frequency range from 30 kHz to 800 MHz for ionic liquids containing BF 4 – , PF 6 – , TFSI – , and FSI – anions and EMIM + cation. By combining experimental R 1 H and R 1 F NMR dispersion (NMRD) profiles with relaxation models for both dipolar spin interactions and chemical shift anisotropy (CSA) contributions, we demonstrate that CSA is needed to accurately describe the R 1 F relaxation behavior above ∼300 MHz, the extent of which depends on the anion structure. These findings challenge the long-standing assumption that dipolar contribution is the main source of 19 F relaxation in these systems and highlight the importance of including CSA to accurately interpret 19 F relaxation in ionic liquids, particularly at high frequencies. This work provides new insights into the molecular dynamics of fluorine-containing species.

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

Probing the electronic structure and spectroscopy of pyrrolyl and imidazolyl radicals using high-resolution photoelectron imaging of cryogenically cooled anions

High-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled pyrrolide and imidazolide anions are used to probe the electronic structure and spectroscopy of pyrrolyl and imidazolyl radicals. The high-resolution data allow the ground state vibronic structures of the two radicals to be completely resolved, yielding accurate electron affinities of 2.1433 ± 0.0008 eV and 2.6046 ± 0.0006 eV for pyrrolyl and imidazolyl radicals, respectively. Fundamental frequencies for eight vibrational modes of pyrrolyl and ten vibrational modes of imidazolyl are measured, including several nonsymmetric Franck–Condon-forbidden modes. Two electronic excited states are also observed for the two radicals, displaying diffuse spectral features in both systems. The observations of nonsymmetric vibrational modes in the ground states and the diffuse excited state features provide strong evidence for vibronic couplings between the ground state and the two close-by excited states. The 2-pyrrolide isomer is also observed as a minor species from the electrospray ionization source and the electron affinity of 2-pyrrolyl is measured to be 1.6690 ± 0.0030 eV along with five vibrational frequencies. Even though the HOMOs of both pyrrolide and imidazolide anions are p orbitals, photodetachment spectroscopy reveals completely different threshold behaviors for the two anions: a d-wave-dominated spectrum for pyrrolide and an s-wave-dominated spectrum for imidazolide. Furthermore, the current study provides a wealth of electronic and spectroscopic information, which is ideal to compare with more accurate vibronic coupling calculations for these two important radicals, as well as interesting information about the photodetachment dynamics of the two anions.

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

Relationship of the Molecular Structure and Transport Properties of Imide-Based Lithium Salts of “Acetonitrile/Water-in-Salt” Electrolytes

“Water-in-salt” (WIS) electrolytes exhibit excellent safety and electrochemical performance. However, they possess high concentrations, relatively low diffusion coefficient, and high viscosity. “Acetonitrile/water in salt” (AWIS) electrolytes can overcome the disadvantages of WIS electrolytes. Under relatively low concentrations, AWIS electrolytes show good electrochemical performance comparable to WIS electrolytes and low conductivity. Herein, we investigate the relationship between the solvation structures and the transport properties using small-angle X-ray scattering and molecular dynamics simulation. We observed two solvation behaviors of AWIS: anions dissolved in acetonitrile forming small acetonitrile/anion clusters and additional water further dissolving the small acetonitrile/anion clusters. The introduction of acetonitrile weakens the water–solute interaction and enhances the cation–anion interaction, which results in an enhanced dynamical slowdown as the concentration increases. In conclusion, this work provides molecular-level understanding of the connection between two-stage solvation structures and transport properties for imide-based lithium salt solutions.

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

On the Dynamics of the Carbon–Bromine Bond Dissociation in the 1-Bromo-2-Methylnaphthalene Radical Anion

This paper studies the mechanism of electrochemically induced carbon–bromine dissociation in 1-Br-2-methylnaphalene in the reduction regime. In particular, the bond dissociation of the relevant radical anion is disassembled at a molecular level, exploiting quantum mechanical calculations including steady-state, equilibrium and dissociation dynamics via dynamic reaction coordinate (DRC) calculations. DRC is a molecular-dynamic-based calculation relying on an ab initio potential surface. This is to achieve a detailed picture of the dissociation process in an elementary molecular detail. From a thermodynamic point of view, all the reaction paths examined are energetically feasible. The obtained results suggest that the carbon halogen bond dissociates following the first electron uptake follow a stepwise mechanism. Indeed, the formation of the bromide anion and an organic radical occurs. The latter reacts to form a binaphthalene intrinsically chiral dimer. This paper is respectfully dedicated to Professors Anny Jutand and Christian Amatore for their outstanding contribution in the field of electrochemical catalysis and electrosynthesis.

1-bromo-2-methylnaphthalene↗