Search NASA⌕ Search

SEARCH · Search NASA

Results for “ionic bonding”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Efficient Implementation of NOCI-MP2 Using the Resolution of the Identity Approximation with Application to Charged Dimers and Long C–C Bonds in Ethane Derivatives

An efficient implementation of the perturb-then-diagonalize nonorthogonal configuration interaction method with second-order Møller-Plesset perturbation theory (NOCI-MP2) is introduced. Relative to other low scaling multireference perturbation theories, NOCI-MP2 often requires a much smaller active space because of the use of nonorthogonal reference configurations. Reworking the NOCI-MP2 equations with the resolution of the identity (RI) approximation enables the method to have the same memory requirements and computational scaling as single reference RI-MP2. The working equations are extended to include single substitutions as required when the reference determinants do not satisfy the Hartree-Fock equations. A detailed computational algorithm is presented along with timings to establish the performance of the implementation. NOCI-MP2 is applied to the binding energy and charge resonance energy in dication and monocation π dimers, as well as didiamantane ethane, and hexaphenylethane. A well-defined set of nonorthogonal determinants are obtained using absolutely localized molecular orbitals (ALMOs), as solutions to the self-consistent field for molecular interactions (SCF-MI) equations corresponding to covalent and ionic determinants. Agreement with experimental information where available, and other multireference methods, is satisfactory, with the use of an 0.3 au level shift to guard against large MP2 amplitudes. For didiamantane ethane and hexaphenylethane, large dispersion forces help stabilize the molecules despite the steric repulsion. However, in the case of hexaphenylethane, the energy penalty from the geometric distortion of the fragments critically weakens the bond.

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

Selective Lanthanide-Organic Catalyzed Depolymerization of Nylon-6 to ϵ-Caprolactam

We report nylon-6 is selectively depolymerized to the parent monomer ϵ-caprolactam by the readily accessible and commercially available lanthanide trisamido catalysts Ln(N(TMS) 2 ) 3 (Ln = lanthanide). The depolymerization process is solvent-free, near quantitative, highly selective, and operates at the lowest Nylon-6 to ..epsilon..-caprolactam depolymerization temperature reported to date. The catalytic activity of the different lanthanide trisamides scales with the Ln 3+ ionic radius, and this process is effective with post-consumer Nylon-6 as well as with Nylon-6 + polyethylene, polypropylene or polyethylene terephthalate mixtures. Experimental kinetic data and theoretical (DFT) mechanistic analyses suggest initial deprotonation of a Nylon terminal amido N-H bond, which covalently binds the catalyst to the polymer, followed by a chain-end back-biting process in which ϵ-caprolactam units are sequentially extruded from the chain end.

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

Salt-Induced Polymorphs Observed in Colloidal Single Crystals

Polymorphs are solid materials with the same chemical composition but different crystallographic structures. A unique aspect of polymorphs is that they exhibit different physical properties, such as solubility, melting point, density, color, hardness, and bioavailability. Here, we synthesized polymorphs of colloidal crystals engineered with DNA by slow-cooling gold nanoparticle-core programmable atom equivalents (PAEs, particles with DNA sequences that control their bonding characteristics) under salt concentrations ranging from 0.5 to 4 M NaCl. This approach yielded a diverse set of single-crystalline phases with cubic, tetragonal, and hexagonal lattice symmetries. The structural transitions observed here arise solely from the modulation of interparticle repulsion via ionic strength and thermal processing. Notably, in certain cases, we observed diffusionless phase transformations, wherein the superlattices evolve from cubic to lower-symmetry tetragonal lattices. By tuning the thermal stability and salt concentration, we captured intermediate, metastable body-centered tetragonal structures during the slow-cool process, indicating that subtle changes in free energy can direct crystallization to low-symmetry phases. In conclusion, this study demonstrates that thermal and ionic parameters can be tuned to access and stabilize colloidal crystal polymorphs with emergent structures and interesting functional properties.

Colloidal crystallization↗
DOE OSTI2022

Two- and three-body fragmentation of multiply charged tribromomethane by ultrafast laser pulses

We investigate the two- and three-body fragmentation of tribromomethane (bromoform, CHBr 3 ) resulting from multiple ionization by 28-femtosecond near-infrared laser pulses with a peak intensity of 6 × 10 14 W cm -2 . The analysis focuses on channels consisting exclusively of ionic fragments, which are measured by coincidence momentum imaging. The dominant two-body fragmentation channel is found to be Br + + CHBr 2 +. Weaker HBr + + CBr 2 +, CHBr + + Br 2 +, CHBr 2+ + Br 2 +, and Br + + CHBr 2 2+ channels, some of which require bond rearrangement prior to or during the fragmentation, are also observed. The dominant three-body fragmentation channel is found to be Br + + Br + + CHBr + . This channel includes both concerted and sequential fragmentation pathways, which we identify using the native frames analysis method. We compare the measured kinetic energy release and momentum correlations with the results of classical Coulomb explosion simulations and discuss the possible isomerization of CHBr 3 to BrCHBr–Br (iso-CHBr 3 ) prior to the fragmentation.

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

Dynamic Mixing Behaviors of Ionically Tethered Polymer Canopy of Nanoscale Hybrid Materials in Fluids of Varying Physical and Chemical Properties

An emerging area of sustainable energy and environmental research is focused on the development of novel electrolytes that can increase the solubility of target species and improve subsequent reaction performance. Electrolytes with chemical and structural tunability have allowed for significant advancements in flow batteries and CO 2 conversion integrated with CO 2 capture. Liquid-like nanoparticle organic hybrid materials (NOHMs) are nanoscale fluids that are composed of inorganic nanocores and an ionically tethered polymeric canopy. NOHMs have been shown to exhibit enhanced conductivity making them promising for electrolyte applications, though they are often challenged by high viscosity in the neat state. In this study, a series of binary mixtures of NOHM-I-HPE with five different secondary fluids, water, chloroform, toluene, acetonitrile, and ethyl acetate, were prepared to reduce the fluid viscosity and investigate the effects of secondary fluid properties (e.g., hydrogen bonding ability, polarity, and molar volume) on their transport behaviors, including viscosity and diffusivity. We report our results revealed that the molecular ratio of secondary fluid to the ether groups of Jeffamine M2070 ($λ_{\text{SF}}$) was able to describe the effect that secondary fluid has on transport properties. Our findings also suggest that in solution, the Jeffamine M2070 molecules exist in different nanoscale environments, where some are more strongly associated with the nanoparticle surface than others, and the conformation of the polymer canopy was dependent on the secondary fluid. This understanding of the polymer conformation in NOHMs can allow for the better design of an electrolyte capable of capturing and releasing small gaseous or ionic species.

25 ENERGY STORAGE↗
DOE OSTI2023

DFT-based investigation of solvation of Nd(III)/Yb(III) cations in room-temperature ionic-liquid

We report a DFT study on the solvation of bare rare-earth (RE) cations [Nd(III) and Yb(III)] in the room-temperature ionic-liquid (RTIL) based on 1,3-dimethyl-imidazolium + , PF 6 - , [MMI][PF 6 ]. In the present article, we aim to investigate whether the chosen RTIL can preferentially solvate any of the RE cations under study. First, the RTIL binding to the RE cation is studied in the gas phase, and then explored with continuum solvation model employing RTIL parameters. First, we considered the formation of the first solvation shell, where the PF 6 - anions directly bond with the Ln(III) cation. We then further surrounded the first solvation shell with [MMI]+ cations to form the second solvation shell. The stability of PF 6 - coordinated complexes is studied by calculating the binding energy values. The number of PF 6 - anions for both Ln(III) cations starts with three ligands and goes until the maximum binding energy in the RTIL medium is reached. The coordination number and binding modes of PF 6 - depend on the size of the RE cation. Comparing the binding energy values between the RE cations for the first solvation shell complexes, it is noticed that Yb-complexes have relatively greater binding energy than Nd-complexes. We have further performed a Boltzmann population analysis to find out the most dominant conformer among each category of PF 6 - coordinated complexes. A study using Natural Population Analysis shows that after complexation with PF 6 - the charge on the Yb-centers lower to a greater extent than Nd-centers, implying stronger bonding between Yb and PF 6 - , which is in harmony with the binding energy analysis. Overall, the computational investigation provides an in-depth understanding of the complexation phenomena of RE cations in RTIL, which can be useful for the practical separation of RE cations using RTIL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Atom Probe Tomography Unveils Formation Mechanisms of Wear-Protective Tribofilms by ZDDP, Ionic Liquid, and Their Combination

The development of advanced lubricant additives has been a critical component in paving the way for increasing energy efficiency and durability for numerous industry applications. However, the formation mechanisms of additive-induced protective tribofilms are not yet fully understood because of the complex chemomechanical interactions at the contact interface and the limited spatial resolution of many characterizing techniques currently used. In this paper, the tribofilms on a gray cast iron surface formed by three antiwear additives are systematically studied; a phosphonium-phosphate ionic liquid (IL), a zinc dialkyldithiophosphate (ZDDP), and an IL+ZDDP combination. All three additives provide excellent wear protection, with the IL+ZDDP combination exhibiting a synergetic effect, resulting in further reduced friction and wear. Atom probe tomography (APT) and scanning transmission electron microscopy (STEM) imaging and electron energy loss spectroscopy (EELS) were used to interrogate the subnm chemistry and bonding states for each of the tribofilms of interest. The IL tribofilm appeared amorphous and was Fe, P, and O rich. Wear debris particles having an Fe-rich core and an oxide shell were present in this tribofilm and a transitional oxide (Fe 2 O 3 )-containing layer was identified at the interface between the tribofilm and the cast iron substrate. The ZDDP+IL tribofilm shared some of the characteristics found in the IL and ZDDP tribofilms. Finally, tribofilm formation mechanisms are proposed on the basis of the observations made at the atomic level.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Stopping power beyond the adiabatic approximation

Energetic ions traveling in solids deposit energy in a variety of ways, being nuclear and electronic stopping the two avenues in which dissipation is usually treated. This separation between electrons and ions relies on the adiabatic approximation in which ions interact via forces derived from the instantaneous electronic ground state. In a more detailed view, in which non-adiabatic effects are explicitly considered, electronic excitations alter the atomic bonding, which translates into changes in the interatomic forces. In this work, we use time dependent density functional theory and forces derived from the equations of Ehrenfest dynamics that depend instantaneously on the time-dependent electronic density. With them we analyze how the inter-ionic forces are affected by electronic excitations in a model of a Ni projectile interacting with a Ni target, a metallic system with strong electronic stopping and shallow core level states. We find that the electronic excitations induce substantial modifications to the inter-ionic forces, which translate into nuclear stopping power well above the adiabatic prediction. Particularly, we observe that most of the alteration of the adiabatic potential in early times comes from the ionization of the core levels of the target ions, not readily screened by the valence electrons.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries

Alloying of anions is a promising engineering strategy for tuning ionic conductivity in halide-based inorganic solid electrolytes. We explain the alloying effects in Li 3 InBr 6-x Cl x , in terms of strain, chemistry, and microstructure, using first-principles molecular dynamics simulations and novel electronic structure analysis. We find that strain and bond chemistry can be tuned through alloying and affect the activation energy and maximum diffusivity coefficient. The similar conductivities of the x=3 and x=6 compositions can be understood by assuming the alloy separates into Brrich and Cl-rich regions. Phase-separation increases diffusivity at the interface and in the expanded Cl-region, suggesting microstructure effects are critical.

25 ENERGY STORAGE↗
DOE OSTI2018

On the relationship between the structural and volumetric properties of solvated metal ions in O -donor solvents using new structural data in amide solvents

The structures of the N , N -dimethylformamide (dmf), N , N -dimethylacetamide (dma), and N , N -dimethylpropionamide (dmp) solvated strontium and barium ions have been determined in solution using large angle X-ray scattering and EXAFS spectroscopy. The strontium ion has a mean coordination number (CN) between 6.2 and 6.8, and the barium ion has a mean CN between 7.1 and 7.8 in these amide solvents. The non-integer numbers indicates that equilibria between different coordination numbers and geometries exist in these systems. Structural information of the alkali, alkaline earth, and selected transition metal and lanthanoid( III ) ions, and the halide ions in water, methanol, ethanol, dimethylsulfoxide, formamide, dmf and dma has been combined with previously reported standard partial molar volumes, V 0 . The ionic radii and charge densities (charge/ionic volume), and corresponding V 0 values have been used to gain information on the relationship between structural and volumetric properties. For the structure-breaking ions, i.e. the alkali metal and halide ions, there is an almost linear relationship between the ionic radius and V 0 . On the other hand, for the structure-making ions, here the alkaline earth, transition metal and lanthanoid( III ) ions, a linear relationship is observed between the charge density and V 0 . Solvents with a well-defined bulk structure through hydrogen bonding, specifically, water, methanol and ethanol, will be more contracted through solvation than aprotic solvents, as the space between the solvent molecules is lost as a result of the hydrogen bonding. In this respect, methanol stands out as the most compressed solvent participating in solvation compared to its bulk structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2021

Hydrogen Plasma Reduction

Hydrogen plasma increases efficiency by strategically using energy to break bonds within the regolith to liberate oxygen instead of heating the entire bed of regolith. The energy used by the plasma system would be imparted into the H2 gas, forming highly energetic ions, electrons, and neutrals that would interact with the regolith surface. The energized atomic and ionic H2 provide the energy needed to make reduction of SiO2 (Silicon Dioxide) and other regolith mineral oxides favorable. What’s more, the high-energy plasma interaction occurs in a small, localized volume, and thus requires relatively little energy. The lunar regolith is well-suited for the process as the fine particles naturally available provide a high surface area for the plasma to interact with. The process would require a system to collect the regolith composed of metal oxides (MxOy) and load it into a reactor. An H2 plasma would pass over the surface (potentially at a low pressure, reducing complexity of the system as it would not require large increases in pressure from the lunar vacuum), then the gases from the plasma reaction would be collected and processed, and the spent regolith would be carried away. The gross reaction temperature would be near ambient (due to the localized nature of the plasma), eliminating the necessity of a regolith heating mechanism or handling of molten regolith. Also, the H2 used in the plasma could be subsequently recovered from the water produced by the plasma reaction. Thus, this approach would not require significant amounts of added commodities.

Elspeth Petersen↗
DOE OSTI2016

Dynamic acid/base equilibrium in single component switchable ionic liquids and consequences on viscosity

The deployment of transformational non-aqueous CO 2 -capture solvent systems is encumbered by high viscosity even at intermediate uptakes. Using single-molecule CO 2 binding organic liquids as a prototypical example, we identify the key molecular features controlling bulk liquid viscosity and CO 2 uptake kinetics. Fast uptake kinetics arise from close proximity of the alcohol and amine sites that are involved in CO 2 binding. This process results in the concerted formation of a Zwitterion containing both an alkylcarbonate and a protonated amine. The hydrogen bonding between the two functional groups ultimately determines the solution viscosity. Based on molecular simulation, this work reveals options to significantly reduce viscosity with molecular modifications that shift the proton transfer equilibrium towards a neutral acid/amine species as opposed to the ubiquitously accepted Zwitterionic state. Lastly, the molecular design concepts proposed here, for the alkyl-carbonate systems, are readily extensible to other CO 2 capture technologies, such as the carbamate- or imidazole-based solvent chemistries.

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

Ionic liquid electrolyte for lithium-ion batteries

The ionic liquids disclosed herein are salts comprising a nitrogen or phosphorus such as a quaternary ammonium ion, a quaternary phosphonium ion, or an N-alkylated nitrogen heterocycle, and which include at least one functional substituent, e.g., a fluoro, cyano, carbonate ester, an alkenyl group, or an alkynyl group bonded to a carbon atom the cation. In a preferred embodiment, the cation is represented by the structure of Formula (I) as described herein.

Zhang, Zhengcheng↗
DOE OSTI2018

X-ray-Induced Fragmentation of Imidazolium-Based Ionic Liquids Studied by Soft X-ray Absorption Spectroscopy

In this work, we investigated the X-ray absorption spectroscopy (XAS) fingerprint of EMImTFSI ionic liquid (IL) and its fragmentation products created by X-ray irradiation. To accomplish this, we used an open geometry where an IL droplet is directly exposed in the vacuum chamber and an enclosed geometry where the IL is confined in a cell covered by an X-ray transparent membrane. In the open geometry, the XAS signature was stable and consistent with experimental and theoretical spectra reported in the literature. In contrast, when the IL is enclosed, its XAS evolves continuously under X-ray illumination due to the accumulation of volatile fragmentation products inside the closed cell, while they evaporate in the open geometry. The changes in the XAS from the core levels of relevant elements (C, N, S, F) together with density functional theory calculations allowed us to identify the chemical nature of the fragment products and the chemical bonds most vulnerable to rupture under soft X-ray irradiation.

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

Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO 2

The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO 2 (400 ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO 2 insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400 ppm) CO 2 from gas mixtures via O$-$C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using 13 C-labeled CO 2 sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40 kJ mol -1 between CO 2 and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO 2 release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO 2 insertion. In conclusion, the as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO 2 in crystalline scaffolds.

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

Ab initio molecular dynamics simulation of supercritical aqueous ionic solutions: Spectral diffusion of water in the vicinity of Br¯ and I¯ ions

Supercritical aqueous ionic solutions containing bromide (Br¯) and iodide (I¯) ions have been studied using Car-Parrinello molecular dynamics simulation at two different concentrations and at two different densities. The time dependent trajectory has been used for calculating vibrational spectral diffusion, structural properties and, for other dynamical properties such as hydrogen bond dynamics, orientational relaxation and residence dynamics. The vibrational spectral diffusion of fluctuating OD stretch mode inside the solvation shell of the ions and in the bulk has been studied using frequency-frequency time correlation function. Hydrogen bond dynamics, orientational relaxation and residence dynamics of Sc-water have been investigated using population correlation function approach. The water molecules inside the solvation shell of Br¯ and I¯ ions are found to show complex molecular dynamics in comparison to the water-water dynamics. The concentration dependent spectral diffusion has been observed and it occurs in multiple time scales in the solvation shell of Br¯ and I¯ ions. Here, at supercritical condition, the ion-water hydrogen bond shows faster dynamics with respect to the same at ambient condition and slower dynamics with respect to the water-water hydrogen bond dynamics at supercritical condition.

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

Preparation of ternary hydrophobic magnetic deep eutectic solvents and an investigation into their physicochemical properties

Hydrophobic magnetic deep eutectic solvents (HMDESs) are considered a subclass of DESs comprised of a hydrogen bond acceptor (HBA), hydrogen bond donor (HBD), and a metal halide salt. These DESs can be easily manipulated by an external magnet and employed in numerous applications including liquid–liquid extractions and catalysis. In this work, a total of forty-six (46) HMDESs were prepared and their physicochemical properties studied. Six structurally unique ionic and non-ionic HBAs were combined with lanthanide and transition metal halide salts and twelve different HBDs to prepare room temperature eutectic solvents. The viscosities of HMDESs ranged from 46 centipoise (cP) to 124,600 cP at 23 °C. Their magnetic susceptibilities, studied by superconducting quantum interference device (SQUID) magnetometry and a magnetic susceptibility balance, varied from 3.03 Bohr magnetons (μB) to 9.32 μB when the type of metal halide salt and its molar ratio were varied. Thermal stabilities ranged from 151.1 °C to 308.5 °C at 5% mass loss. Further, all HMDESs comprised of ionic HBA were observed to be insoluble in hexane. This study demonstrates that the physicochemical properties of HMDESs can easily be tailored by varying the DES constituents as well as their molar ratio. The structural tunability of these solvents make them highly attractive candidates for a plethora of applications ranging from extractions to electrochromic applications, where HMDESs can be easily manipulated by an external magnetic field.

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

Ion Mobility Spectrometry Characterization of the Intermediate Hydrogen-Containing Gold Cluster Au7(PPh3)7H52+

We employ ion mobility spectrometry and density functional theory to determine the structure of Au7(PPh3)7H52+ (PPh3 = triphenylphosphine) which was recently identified by high mass resolution mass spectrometry. Experimental ion-neutral collision cross sections represent the momentum transfer between the ionic clusters and gas molecules averaged over the relative thermal velocities of the colliding pair, thereby providing structural insights. Theoretical calculations indicate the geometry of Au7(PPh3)7H52+ is similar to Au7(PPh3)7+, with three hydrogen atoms bridging two gold atoms and two hydrogen atoms forming single Au–H bonds. Collision induced dissociation products observed during IMS experiments reveal that smaller hydrogen containing clusters may be produced through fragmentation of Au7(PPh3)7H52+. Our findings indicate that hydrogen containing species like Au7(PPh3)7H52+ act as intermediates in the formation of larger phosphine ligated gold clusters. These results advance the understanding and ability to control the mechanisms of size selective cluster formation which is necessary for scalable synthesis of clusters with tailored properties. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. M.A.H. acknowledges support from the DOE Science Undergraduate Laboratory Internship (SULI) program. H.H. acknowledges support from the DOE Office of Workforce Development for Teachers and Scientist (WDTS) under the Visiting Faculty Program (VFP). The efforts of K.A.M. and B.H.C. were supported by the Defense Threat Reduction Agency (Grant No. HDTRA1-14-1-0023). The research was performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for DOE under Contract DE-AC05-76RL01830.

Ligare, Marshall R.↗