Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ionic interactions”

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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Ion transport in non-aqueous electrolyte mixtures of zinc chloride deep eutectic solvent (DES) and molecular solvents

For this work, the ion dynamics of null solvents 1ZnCl 2 :4EtG and 1ChCl:1ZnCl 2 :6EtG incorporating 1M water, propylene carbonate (PC) or acetonitrile (AcN) were investigated using 1 H NMR spectra and spin-lattice relaxation time (T 1 ) measurements combined with ionic conductivity, density, and viscosity, all as a function of temperature. Results show that the inclusion of all co-solvents increased the available free volume of the mixtures and followed the trend H 2 O ≤ PC < AcN. 1 H NMR spectra and T 1 inferred the presence of multiple ionic species with varying rates of mobilities. These dynamic heterogeneities were displayed by the broad T 1 minima – especially for the 1ZnCl 2 :4EtG mixtures – and asymmetrically broadened linewidths. T 1 results also revealed selective interaction sites between the hydrogen bond donors and acceptors, as well as with the co-solvents.

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

Self–Healing and Stretchable Molecular Ferroelectrics with High Expandability

The interplay between crystal ordering and stretchability is frequently encountered in contemporary materials science, particularly in the case of ferroelectrics. The inherent dilemma arises when these materials need to withstand repetitive mechanical deformations or stretching without sacrificing their crystal integrity, all while retaining their remarkable ferroelectric properties and even exhibiting self-healing capabilities. This complexity further presents a significant challenge in the design and engineering of mechanically rigid molecular ferroelectric crystals, particularly for applications where both precise crystalline structure and mechanical adaptability are crucial. In this study, the humidity-controlled expansion and contraction, dissolution, and recrystallization of a self-assembled molecular ferroelectric-in-hydrogel framework are reported. Self-healing ferroelectric-in-hydrogel networks exhibit a recyclable humidity-tailored ionic conductivity from 2.86 × 10 –6 to 1.36 × 10 –5 S cm –1 , facilitating the stretchable piezoelectric sensing. Additionally, the dynamic bond reforming interactions are observed, leading to the tailoring of Young's modulus from 452 to 170 MPa, maintaining ferroelectricity under a strain of 20% with a piezoelectric coefficient of 15.7 pC N –1 . Upon lattice contraction, the molecular contacts undergo reforming, leading to the restoration of stretchable ferroelectrics/piezoelectrics and paving the way for stretchable bioelectronics for full-body motion monitoring. The capabilities highlighted here open avenues for stretchable and self-healing ferroelectric-in-hydrogel bioelectronic technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dynamical Ion Correlations in Polymer and Membrane Electrolytes: Recent Advances and Open Questions

Ion transport in polymer and membrane electrolytes is often described using uncorrelated models like the Nernst–Einstein (NE) approximation, which link conductivity, transference number, and salt diffusivity to individual ion mobilities. However, growing evidence shows that dynamical ion correlations─arising from ion pairing, polymer-mediated coupling, confinement, and electrostatic interactions─can substantially alter macroscopic transport properties. The Onsager transport formalism offers a rigorous framework to quantify these effects via cross-correlated ionic displacements. This Perspective highlights how such correlations manifest across dry and hydrated systems, including salt-doped polymers, block copolymers, hydrogels, and ion-exchange membranes. Here, we examine key physical origins, the influence of salt chemistry and polymer structure, and open questions in measuring and controlling correlated motion. Embracing correlation-aware design enables new pathways to optimize conductivity, transference number, and selectivity─shifting the focus from individual ion mobility to engineered collective dynamics for next-generation electrolytes in energy storage and separations.

Charge transport↗
DOE OSTI2023

Systematic observations of enhanced oil recovery and associated changes at carbonate-brine and carbonate-petroleum interfaces

Enhanced oil recovery (EOR) from carbonates is obtained by injection of controlled ionic strength brines containing “active ions” (e.g., SO 4 2- , Mg 2+ , Ca 2+ ). It is generally believed that this occurs through the interaction of the active ions at the carbonate-brine interface (e.g., within a thin brine layer separating the petroleum and the carbonate phases). Here, in-situ observations show how one active ion, SO 4 2- , alters behavior at the carbonate-petroleum interface. Displacement of petroleum from initially oil-wet carbonate rocks using brines with variable SO 4 concentrations systematically changes oil recovery, in situ contact angles, and connectivity of the oil phase, confirming that the active ion alters interactions at the oil/brine/carbonate interface, as expected. Measurements of model calcite-fluid interfaces show that there is no measurable sorption of SO 4 to carbonate-brine interfaces but reveals that the carbonate-petroleum interface is altered by previous exposure to SO 4 -containing brines. These results suggest that EOR in carbonates is controlled indirectly by active ions. We propose that this may be due to a reduced oleophilicity of the carbonate caused by chemical complexation between the active ion and petroleum’s acidic and basic functional groups. This mechanism explains how both anions and cations act as active ions for EOR in carbonates.

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

Alkali-induced catalytic tuning at metal and metal oxide interfaces

Alkali metals have been recognized as effective promoters in heterogeneous catalysis, capable of enhancing catalytic activity and tuning product distributions. Over the past few decades, significant efforts have been made aiming to reveal the mechanisms underlying the promoting effect of alkalis. However, the roles that alkali metals play in the catalytic process remain elusive due to challenges in capturing their catalytic behaviours upon exposure to reactive environments. This review summarizes recent surface science and theoretical studies of alkali (potassium, cesium)-decorated metal and metal oxide model catalysts, revealing the crucial tuning by alkalis of activity and selectivity for CO 2 hydrogenation. The analysis of electronic structures identifies the selective binding mechanism of the positively charged alkali ions on the surface, being able to reduce the surface work function and lead to strong electron polarization on the surfaces. Depending on the alkali–support interaction, the deposition of alkalis can selectively modify the bindings of reaction intermediates involved in CO 2 hydrogenation via the interplay among the ionic, covalent and electrostatic tunings. As a result, CO 2 can be effectively activated and converted into diverse products at the alkali–support interface, ranging from formic acid to methanol and ethanol. The identified selective bond-tuning advances the application of alkalis in promoting catalytic activity and controlling catalytic selectivity at alkali–support interfaces.

03 NATURAL GAS↗
DOE OSTI2020

Designing electrolytes with polymerlike glass-forming properties and fast ion transport at low temperatures

Significance Liquid electrolytes with thermophysical properties analogous to solid polymers, but with exceptional liquidlike ionic conductivities, are formed spontaneously when moderate amounts (≤1 M) of inorganic salts coordinate strongly with small molecules in a conventional aprotic solvent. Specifically, we report that electrolytes composed of the cyclic liquid ether, dioxolane (DOL), and containing the simple salt LiNO 3 are able to completely bypass the liquid → crystalline solid thermal transition, and to exhibit abnormally high bulk and interfacial ionic conductivities down to temperatures as low as −50 °C. Through physical, spectroscopic, and ion-transport measurements it is shown that strong interactions between LiNO 3 and DOL distort bonds in DOL, couple motions of individual solvent molecules, and lower the thermodynamic activity of the electrolyte.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Verification Testing of OLI Systems Mixed Solvent Electrolyte Model for the Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 ) System to High Ionic Strength at 25°C

This technical report summarizes model verification results and summary statistics for 41 evaporite mineral solubility cases evaluated by Savannah River National Laboratory using OLI Systems’ aqueous electrolyte thermodynamic modeling software. The 41 verification cases containing a total of 60 solubility curves comprise mineral solubility data from low to high ionic strength at 25°C for the eight-component system Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 O as reported by Harvie et al. (1984). Thermodynamic calculations were executed using OLI Systems’ Stream Analyzer computation module within the OLI Studio software platform (Ver. 11.0, Rev. 11.0.1.9). The Mixed Solvent Electrolyte (MSE) thermodynamic framework was chosen for this investigation because of its superiority in modeling high ionic-strength inorganic salt solutions and actinide redox chemistry and solubility, both of which are relevant to the geological repository conditions at the Waste Isolation Pilot Plant in Carlsbad, New Mexico. Mineral solubility data in various inorganic salt solutions were digitized and extracted from figures generated by Harvie et al. (1984). For each of the 60 solubility curves, a case-specific chemistry model and input file were generated in OLI Studio using OLI Stream Analyzer and the MSE (H 3 O + ion) public databank provided by OLI Systems. Model simulation results were exported to Microsoft Excel to calculate summary statistics and to generate graphs comparing the OLI model predictions to the solubility data. Summary statistics include residuals (model – data) and concordance (accuracy × precision, where precision is indicated by the Pearson correlation coefficient and accuracy accounts for bias and scale differential). Private databanks were not developed, and activity coefficient model regressions were not performed to improve OLI model fits to the data. Of the 41 model verification plots, 83% have a mean of the percent residuals less than or equal to 25%. Similarly, 75% display a concordance greater than or equal to 0.75. Only seven of the 41 verification plots fail to show good agreement between the model and data. Of these seven, three are relevant to the WIPP repository because they involve the Mg-OH-Cl-SO 4 -CO 3 aqueous system. The remaining four address salt solubilities at the pH extremes (strong acid and strong base). It should be noted that in two of the three Mg-OH-Cl-SO 4 -CO 3 system cases, the regressed Harvie et al. (1984) solubility curve also deviated from the data. Lack of agreement between the OLI model-predicted solubility curves and the data is attributable to one or more of the following: specific solid species are not included in the OLI MSE databank; there is significant variation among the different solubility datasets chosen by Harvie et al. (1984); the OLI MSE model’s thermodynamic parameters were determined using different solubility datasets; and the activity coefficient parameters for certain relevant ion-ion and ion-molecule pairs have not been optimized via data regression. Two recommendations for future work are to (1) evaluate solubility data for the Mg-OH-Cl-SO 4 -CO 3 system at high ionic strength and, if necessary, develop a private OLI MSE database that includes missing species and, where necessary, regressed standard state properties and interaction parameters; (2) perform similar verification testing of the OLI model for actinide solubility data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Ionic Contraction across the Lanthanide Series Decreases the Temperature-Induced Disorder of the Water Coordination Sphere

In liquid, temperature affects the structures of lanthanide complexes in multiple ways that depend upon complex interactions between ligands, anions, and solvent molecules. The relative simplicity of lanthanide aqua ions (Ln 3+ ) make them well suited to determine how temperature induces structural changes in lanthanide complexes. In this work, we performed a combination of ab initio molecular dynamics (AIMD) simulations and extended X-ray absorption fine structure (EXAFS) measurements, both at 25 and 90 °C, to determine how temperature affects the first- and second-coordination spheres of three Ln 3+ (Ce 3+ , Sm 3+ , and Lu 3+ ) aqua ions. AIMD simulations show first lanthanide coordination spheres that are similar at 25 and 90 °C, more so for the Lu 3+ ion that remains as eight-coordinate than for the Ce 3+ and Sm 3+ ions that change their preferred coordination number from nine (at 25 °C) to eight (at 90 °C). The measured EXAFS spectra are very similar at 25 and 90 °C, for the Ce 3+ , Sm 3+ , and Lu 3+ ions, suggesting that the dynamical disorder of the Ln 3+ ions in liquid water is sufficient such that temperature-induced changes do not clearly manifest changes in the structure of the three ions. Both AIMD simulations and EXAFS measurements show very similar structures of the first coordination sphere of the Lu 3+ ion at 25 and 90 °C.

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

Crosslinked polymeric ionic liquid stationary phases incorporating a combination of silver(I) and copper(II) ions for olefin separations by gas chromatography

The development of efficient and selective olefin separation technologies is a critical challenge within the chemical industry given the high energy demands of conventional cryogenic distillation methods. To address this, the study explores the effectiveness of polymeric ionic liquid (PIL) stationary phases in gas chromatography (GC) that incorporate both silver(I) ([Ag + ]) and copper(II) ([Cu 2+ ]) ions for enhanced olefin separation via π-complexation interactions. Further, the effects of both non-crosslinked and crosslinked PIL stationary phases containing varying ratios of [Ag⁺] and [Cu²⁺] ions were systematically investigated to evaluate their impact on the separation of olefins from paraffins and structurally similar olefins. Retention measurements using a broad range of olefinic probes revealed that [Ag⁺] ions provided stronger and more consistent π-complexation in PIL-based stationary phases, while [Cu²⁺] ions preferentially enhance olefin retention in crosslinked systems. Furthermore, thermal stability studies showed that [Ag + ]-containing PIL stationary phases maintain stable olefin separation efficiency over prolonged exposure under elevated temperatures, while crosslinked PIL stationary phases containing [Cu 2+ ] ions exhibited stronger retention due to increased surface adsorption. These findings provide insight into the tunability of metal–olefin interactions using PIL-based stationary phases and suggest design strategies for achieving thermally stable and highly selective chromatographic separations of unsaturated hydrocarbons.

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

Approach to using 3D laser-induced breakdown spectroscopy (LIBS) data to explore the interaction of FLiNaK and FLiBe molten salts with nuclear-grade graphite

Nuclear graphite has historically been a key component of many nuclear reactor designs and has emerged as key to numerous advanced nuclear reactor design concepts. Molten salt reactors (MSRs) are one broad group of advanced reactor designs currently being pursued by industry for commercialization. Several MSR designs under consideration use graphitic materials that directly interface with a molten salt, whether it is a fuel salt, coolant salt, or both. Therefore, the interaction of graphite materials with molten salts must be understood. To gain this required understanding, a range of data is needed including porosity, strength, and composition as a function of different salt exposure parameters. In this study, a laser-induced breakdown spectroscopy (LIBS) measurement and data analysis methodology was developed to obtain spatially resolved elemental composition information for graphite samples exposed to a molten fluoride salt. Traditional univariate emission line analysis of atomic, ionic, and molecular optical emission signals was coupled via correlation analysis with spectral decomposition of the data using principal component analysis. Elemental depth profiling and elemental mapping were also performed to visualize salt–graphite interactions. LIBS was demonstrated to be useful for measuring key analytes such as fluorine and hydrogen, which are troublesome for other analysis techniques. Evidence for complex behavior was found, thereby demonstrating the usefulness of the developed approach for future systematic studies.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
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 OSTI2025

Ionic Liquids in Analytical Chemistry: Fundamentals, Technological Advances, and Future Outlook

The development of new analytical methods most often focus on novel materials used to impart selectivity or sensitivity to the protocol. Ionic liquids (ILs) are a class of solvents that have been extensively explored as promising materials for various applications and continue to be explored due to their tunable physicochemical properties. These materials possess melting temperatures below 100 °C and can interact with analytes through a multitude of interactions afforded by their readily tunable chemical structure. These interactions include electrostatic, dispersive, hydrogen bonding, π–π, and dipolar interactions and can be modulated or strengthened based on the functional groups present within the chemical structure. ILs consist predominately of organic cations and either inorganic or organic anions, both of which can be functionalized with desired moieties. Common cation and anions found in IL chemical structures are presented in Figure 1. The unique polarity afforded by the ionic structure has also led to their increasing use in areas including sample preparation, chemical separations, electrochemistry, mass spectrometry, and spectroscopy.

Zeger, Victoria R. [Iowa State Univ., Ames, IA (Un↗
DOE OSTI2023

Satellite-Dominated Sulfur L 2,3 X-ray Emission of Alkaline Earth Metal Sulfides

The sulfur L 2,3 X-ray emission spectra of the alkaline earth metal sulfides BeS, MgS, CaS, SrS, and BaS are investigated and compared with spectra calculations based on density functional theory. Very distinct spectral shapes are found for the different compounds. With decreasing electronegativity of the cation, that is, increasing ionic bonding character, the upper valence band width and its relative spectral intensity decrease. These general trends are qualitatively reproduced by the spectra calculations, which give quite an accurate description of the spectral shapes in the upper valence band region. On the low energy side of the sulfur 3s → 2p transition dominating the spectra, we find strong satellites caused by "semi-Auger" decays involving configuration interaction. These satellites, previously believed to be energetically forbidden for sulfur L 2,3 emission and only observed for the L 2,3 emission of Cl to Cr, increase in intensity as the bonding character becomes more ionic and dominate the spectra for SrS and BaS. The intensities, energies, and widths of the satellites vary strongly between the investigated compounds, giving a very specific spectral fingerprint that can be used for speciation analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Insight into the Structural and Emissive Behavior of a Three‐Dimensional Americium(III) Formate Coordination Polymer

Abstract We report the structural, vibrational, and optical properties of americium formate (Am(CHO 2 ) 3 ) crystals synthesized via the in situ hydrolysis of dimethylformamide (DMF). The coordination polymer features Am 3+ ions linked by formate ligands into a three‐dimensional network that is isomorphous to several lanthanide analogs, (e. g., Eu 3+ , Nd 3+ , Tb 3+ ). Structure determination revealed a nine‐coordinate Am 3+ metal center that features a unique local C 3v symmetry. The metal–ligand bonding interactions were investigated by vibrational spectroscopy, natural localized molecular orbital calculations, and the quantum theory of atoms in molecules. The results paint a predominantly ionic bond picture and suggest the metal‐oxygen bonds increase in strength from Nd−O 5 D 1′ → 7 F 0′ emission band is observed and dominates the emission spectrum. This behavior is unusual and is attributed to the C 3v coordination environment of the metal center.

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

CHGNet as a pretrained universal neural network potential for charge-informed atomistic modelling

Large-scale simulations with complex electron interactions remain one of the greatest challenges for atomistic modelling. Although classical force fields often fail to describe the coupling between electronic states and ionic rearrangements, the more accurate ab initio molecular dynamics suffers from computational complexity that prevents long-time and large-scale simulations, which are essential to study technologically relevant phenomena. Here we present the Crystal Hamiltonian Graph Neural Network (CHGNet), a graph neural network-based machine-learning interatomic potential (MLIP) that models the universal potential energy surface. CHGNet is pretrained on the energies, forces, stresses and magnetic moments from the Materials Project Trajectory Dataset, which consists of over 10 years of density functional theory calculations of more than 1.5 million inorganic structures. The explicit inclusion of magnetic moments enables CHGNet to learn and accurately represent the orbital occupancy of electrons, enhancing its capability to describe both atomic and electronic degrees of freedom. We demonstrate several applications of CHGNet in solid-state materials, including charge-informed molecular dynamics in Li x MnO 2 , the finite temperature phase diagram for Li x FePO 4 and Li diffusion in garnet conductors. We highlight the significance of charge information for capturing appropriate chemistry and provide insights into ionic systems with additional electronic degrees of freedom that cannot be observed by previous MLIPs.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Self-sorting in supramolecular assemblies

Supramolecular self-assembly enables living organisms to form highly functional hierarchical structures with individual components self-organized across multiple length scales. This has inspired work on multicomponent supramolecular materials to understand factors behind co-assembly versus self-sorting of molecules. We report here on a supramolecular system comprised of negatively charged peptide amphiphile (PA) molecules, in which only a tiny fraction of the molecules (0.7 mol%) were covalently conjugated to one of two different fluorophores, half to fluorescein isothiocyanate (FTIC) and the other half to tetramethylrhodamine (TAMRA). Confocal microscopy of the system revealed self-sorting of the two different fluorescent PA molecules, where TAMRA PA is concentrated in micron-scale domains while FITC PA remains dispersed throughout the sample. From Förster resonance energy transfer and fluorescence recovery experiments, we conclude that conjugation of the negatively charged FITC to PA significantly disrupts its co-assembly with the 99.3 mol% of unlabeled molecules, which are responsible for formation of micron-scale domains. Conversely, conjugation of the zwitterionic TAMRA causes no such disruption. Interestingly, this dissimilar behavior between FITC and TAMRA PA causes them to self-sort at large length scales in the supramolecular system, mediated not by specific interactions among the individual fluorophores but instead by their different propensities to co-assemble with the majority component. We also found that greater ionic strength in the aqueous environment of the system promotes mixing by lowering the electrostatic barriers involved in self-sorting. Furthermore, our results demonstrate great thermodynamic subtlety in the driving forces that mediate self-sorting versus co-assembly in supramolecular peptide assemblies.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Time-resolved photoelectron imaging of complex resonances in molecular nitrogen

We have used the FERMI free-electron laser to perform time-resolved photoelectron imaging experiments on a complex group of resonances near 15.38 eV in the absorption spectrum of molecular nitrogen, N-2, under jet-cooled conditions. The new data complement and extend the earlier work of Fushitani et al. [Opt. Express 27, 19702-19711 (2019)], who recorded time-resolved photoelectron spectra for this same group of resonances. Time-dependent oscillations are observed in both the photoelectron yields and the photoelectron angular distributions, providing insight into the interactions among the resonant intermediate states. In addition, for most states, we observe an exponential decay of the photoelectron yield that depends on the ionic final state. This observation can be rationalized by the different lifetimes for the intermediate states contributing to a particular ionization channel. Finally, although there are nine resonances within the group, we show that by detecting individual photoelectron final states and their angular dependence, we can identify and differentiate quantum pathways within this complex system.

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

Molecular Dynamics and Free Energy Calculations of Dicyclohexano-18-crown-6 Diastereoisomers with Sm 2+ , Eu 2+ , Dy 2+ , Yb 2+ , Cf 2+ , and Three Halide Salts in Tetrahydrofuran and Acetonitrile Using the AMOEBA Force Field

With the continual development of lanthanides (Ln) in current technological devices, an efficient separation process is needed that can recover greater amounts of these rare elements. Dicyclohexano-18-crown-6(DCH18C6) is a crown ether that may be a promising candidate for Ln separation, but additional research is required. As such, molecular dynamics(MD) simulations have been performed on four divalent lanthanide halide salts(Sm 2+ , Eu 2+ , Dy 2+ , and Yb 2+ ) and one divalent actinide halide salt (Cf 2+ ) bound to three diastereoisomers of DCH18C6. Dy 2+ , Yb 2+ , Cf 2+ , DCH18C6, and tetrahydrofuran (THF) solvent were parameterized for the AMOEBA polarizable force field for the first time, whereas existing parameters for Sm 2+ and Eu 2+ were utilized from our previous efforts. A coordination number (CN) of six for Ln 2+ /An 2+ –O solvated in THF indicated that the cations interacted almost entirely with the oxygens of the polyether ring. A CN of one for Ln 2+ /An 2+ -N solvated in acetonitrile for systems containing iodide suggested that theN atom of acetonitrile was competitive with I – for cation interactions. Fluctuation between five and six CNs for Dy 2+ and Yb 2+ suggested that although the cations remained in the polyether ring, the size of the ring may not be an ideal fit as these cations possess comparatively smaller ionic radii. Gibbs binding free energies of Sm 2+ in all DCH18C6 diastereoisomers solvated in THF were calculated. The binding free energy of the cis-syn-cis diastereoisomer was the most favorable, followed by cis-anti-cis, and then trans-anti-trans. Lastly, two major types of conformation were observed for each diastereoisomer that were related to the electrostatic interactions and charge density of the cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗