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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 1,783 records · Page 99
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Real-time interfacial electron dynamics revealed through temporal correlations in x-ray photoelectron spectroscopy

We present a novel technique to monitor dynamics in interfacial systems through temporal correlations in x-ray photoelectron spectroscopy (XPS) signals. To date, the vast majority of time-resolved x-ray spectroscopy techniques rely on pump–probe schemes, in which the sample is excited out of equilibrium by a pump pulse, and the subsequent dynamics are monitored by probe pulses arriving at a series of well-defined delays relative to the excitation. By definition, this approach is restricted to processes that can either directly or indirectly be initiated by light. It cannot access spontaneous dynamics or the microscopic fluctuations of ensembles in chemical or thermal equilibrium. Enabling this capability requires measurements to be performed in real (laboratory) time with high temporal resolution and, ultimately, without the need for a well-defined trigger event. The time-correlation XPS technique presented here is a first step toward this goal. The correlation-based technique is implemented by extending an existing optical-laser pump/multiple x-ray probe setup by the capability to record the kinetic energy and absolute time of arrival of every detected photoelectron. The method is benchmarked by monitoring energy-dependent, periodic signal modulations in a prototypical time-resolved XPS experiment on photoinduced surface-photovoltage dynamics in silicon, using both conventional pump–probe data acquisition, and the new technique based on laboratory time. The two measurements lead to the same result. The findings provide a critical milestone toward the overarching goal of studying equilibrium dynamics at surfaces and interfaces through time correlation-based XPS measurements.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

NSTXU Diagnostic Disruption Dynamic Loading Represented by Response Spectra

This article presents the results of transient dynamic simulations of loads due to disruption eddy currents on the NSTXU vacuum vessel. Dynamic loading at diagnostic mounting locations is expressed as response spectra derived from the time history results of the dynamic structural simulations of a variety of disruption scenarios. The disruption simulations draw on a history of the project assessments of worst case disruptions for specific components. Major efforts to assess disruption loading have included the vacuum vessel which is the major structural support for the machine, as well as the passive plates (PPs), high harmonic fast wave (HHFW) antenna, and centerstack casing. Each one of these efforts included transient electromagnetic simulations producing time-dependent eddy current Lorentz loads (and in some cases halo loads) which then were applied to time-dependent structural dynamic analyses intended to obtain the proper dynamic amplification factors. In some instances, the EM model and structural model were identical allowing direct transfer of EM forces to the structural model. In other cases, the EM and structural model were not identical and the vector potential (VP) transfer method was used. The results files from these analyses were available (or re-run) to post process in ANSYS Classic time history postprocessor. In conclusion, the ANSYS command is used to create response spectra from time history data at desired points on the vessel.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Dynamic Triggering of Mud Volcano Eruptions During the 2016-2017 Central Italy Seismic Sequence: Triggering of mud volcano eruptions

On 24 August 2016 a seismic event (Mw6.0) was the first of the long Central Italy sequence (ongoing at the end of 2017) of medium-to-high magnitude earthquakes, with nine Mw≥5 up to October 2017, and with about 74.000 seismic events registered after 1 year. The largest was the Mw6.5 30 October 2016 event near Norcia. After the major seismic events, 17 mud volcanoes erupted around Monteleone di Fermo village (Marche region). Mud volcano eruptions generally occurred a few hours to a few days after the main earthquakes, suggesting a seismic triggering. We analyzed the peak ground velocities and dynamic stresses during the three largest earthquakes. We also evaluated the static stress changes in order to assess the potential influence of normal stress changes on the feeder system of the activated mud volcanoes. We find a correlation with dynamic stresses, whereas static stress changes are negligible or negative (with values reaching -0.44 bar, clamping feeder dykes). We conclude that seismic shaking (up to ~3.9 bar during Norcia earthquake) is the dominant driver for these eruptions. Finally, we evaluated the response ratio as a function of the dynamic stress. It increases exponentially with peak dynamic stress varying from <10% for peak dynamic stress >0.3 bar to >50% for peak dynamic stress >2 bar, indicating a link between earthquake shaking and mud volcano activity.

58 GEOSCIENCES↗
DOE OSTI2025

In Situ/Operando Probing of Dynamic Phase Structures of Alumina‐Supported Ultrasmall Copper‐Gold Alloy Nanoparticles Under Reaction Conditions

Abstract The ability to control phase structures and surface sites of ultrasmall alloy nanoparticles under reaction conditions is essential for preparing catalysts by design. This is, however, challenging due to limited understanding of the atomic‐scale phases and their correlation with the ensemble‐averaged structures and activities of catalysts during catalytic reactions. We reveal here a dynamic structural stability of alumina‐supported ultrasmall and equiatomic copper‐gold alloy nanoparticles under reaction conditions as a model system in the in situ/operando study. In situ atomic‐scale morphological tracking under oxygen reveals temperature‐dependent dynamic crystalline‐amorphous dual‐phase structures, showing dynamic stability over an elevated temperature range. This atomic‐scale dynamic phase stability coincides with a “conversion plateau” observed for carbon monoxide oxidation on the catalyst. It is substantiated by the stable lattice ordering/disordering structures and surface sites with oscillatory characteristics shown by operando ensemble‐average structural tracking of the catalyst during the oxidation reaction. The understanding of the atomic‐scale dynamic phase structures in correlation with the ensemble‐average dynamic ordering/disordering phase structures and surface sites provides fresh insights into the unique synergy of the supported alloy nanoparticles. This understanding has implications for the design and structural tuning of active and stable ultrasmall alloy catalysts under elevated temperatures.

Chemistry↗
DOE OSTI2024

Dynamics of High Molecular Weight Cylindrical and Lamellar Block Copolymers with X‐ray Photon Correlation Spectroscopy

Here, the structure and dynamics of polystyrene (PS)-b-poly(ethylene oxide) block copolymers (BCPs) are studied. The BCPs exhibit microphase-separated cylindrical and lamellar morphologies. Structural dynamics are measured with X-ray photon correlation spectroscopy in the small-angle regime. Morphologies and domain sizes are evaluated using small-angle X-ray scattering (SAXS), scanning electron microscopy, and atomic force microscopy. Different solvent processing conditions are investigated. Grain sizes evaluated using SAXS are found to depend on processing only for the rubbery majority BCP. The structural relaxation times are examined as a function of PS volume fraction, temperature, morphology, and structural sizes. Well above the glass transition temperature (T g ) of PS, all samples exhibit stretched autocorrelation decays and diffusive dynamics. Near T g of PS, the dynamics of all samples are anomalous with compressed autocorrelation decays and hyperdiffusive dynamics. This transition occurs at 153 °C or 1.13 T g of PS. In the diffusive regime (at high temperature), structural relaxation times are dependent on the processing method. Near PS T g (at low temperature), structural relaxation times scale with the PS volume fraction. Structural relaxation times do not correlate with grain size, indicating that the out-of-equilibrium state of PS dominates the structural dynamics of these strongly phase-segregated BCPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Multiple dynamic regimes in colloid-polymer dispersions: New insight using X-ray photon correlation spectroscopy

We present an X-ray photon correlation spectros- copy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of col- loids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the satu- ration concentration of added polymer, in which small clusters of nanoparticles form via a short-range depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily gov- erned by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion

36 MATERIALS SCIENCE↗
DOE OSTI2024

Unveiling the Structural Origins of Dynamic Diversity in Pd-Based Metallic Glasses

The β -relaxation is one of the major dynamic behaviors in metallic glasses (MGs) and exhibits diverse features. Despite decades of efforts, the understanding of its structural origin and contribution to the overall dynamics of MG systems is still unclear. Here two palladium-based Pd—Cu—P and Pd—Ni—P MGs are reported with distinct different β -relaxation behaviors and reveal the structural origins for the difference using the advanced X-ray photon correlation spectroscopy and absorption fine structure techniques together with the first-principles calculations. The pronounced β -relaxation and fast atomic dynamics in the Pd—Cu—P MG mainly come from the strong mobility of Cu atoms and their locally favored structures. In contrast, the motion of Ni atoms is constrained by P atoms in the Pd—Ni—P MG, leading to the weakened β -relaxation peak and sluggish dynamics. Finally, the correlation of atomic dynamics with microscopic structures provides a way to understand the structural origins of different dynamic behaviors as well as the nature of aging in disordered materials.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Dynamic Magnetic Features of the Mixed Ising System on the Bilayer Square Lattice

In order to study the dynamic magnetic features of the mixed spin-1 and spin-5/2 Ising system, we have used the mean-field theory (MFT) based on the Glauber-type stochastic dynamics on the bilayer square lattice (BSL). By employing the Master equation, dynamic equations describing the behavior of the system are derived. The average order parameters and dynamic order parameters are studied for different values of exchange interactions, oscillating magnetic field, and temperature. The complete dynamic phase diagrams (DPDs) are obtained for the ferromagnetic/ferromagnetic (FM/FM), ferromagnetic/antiferromagnetic (FM/AFM), and antiferromagnetic/antiferromagnetic (AFM/AFM) interactions in the different planes, and the role of the interaction in the Hamiltonian on the DPDs is explored. It is found that the DPDs display richer dynamic behavior for this mixed Ising system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

On the importance of species immiscibility in mixing-layer dynamics at supercritical pressures

The mixing dynamics of injected propellants is a key factor in determining the ignition performance and combustion-instability response of rocket engines, internal combustion engines, and gas turbines. A key source of uncertainty in the prediction of phase-exchange dynamics is the immiscibility of the injected propellants at supercritical pressure conditions, which induces liquid/vapor phase separation and surface-tension dynamics. While experimental observations indicate the presence of liquid/vapor interfacial structures, this interfacial dynamics is typically neglected in numerical analyses. To address this issue, the objective of the present study is to systematically evaluate the importance of species immiscibility on the phase-exchange dynamics of cryogenic LOX/GH2 mixing layers at typical rocket engine injection conditions. This is accomplished by comparing simulations of (i) a recently developed interface-capturing Regularized-Interface Method (RIM) formulation, and (ii) the commonly employed Diffuse-Interface Method (DIM) formulation. Analysis shows that the interfacial dynamics significantly impact the atomization and mixing of the propellants in the near-injector region, which is not captured by the DIM formulation. The findings of this study extend to other immiscible injection systems, such as LOX/kerosene and hydrocarbon-fuel/air, thereby highlighting the importance of resolving species immiscibility in simulating high-pressure combustion engines.

diffused-interface method↗
DOE OSTI2016

Modeling and simulation framework for dynamic strain localization in elasto-viscoplastic metallic materials subject to large deformations

This study describes a theoretical and computational framework for the treatment of adiabatic shear band formation in rate-sensitive polycrystalline metallic materials. From a computational perspective, accurate representation of strain localization behavior has been a long-standing challenge. In addition, the underlying physical mechanisms leading to the localization of plastic deformation are still not fully understood. The proposed framework is built around an enhanced-strain finite element formulation, designed to alleviate numerical pathologies known to arise in localization problems, by allowing a localization band of given finite width (weak discontinuity) to be embedded within individual elements. The mechanical threshold strength (MTS) model is used to represent the temperature and strain rate-dependent viscoplastic response of the material. This classical flow stress model employs an internal state variable to quantify the effect of dislocation structure evolution (work hardening and recovery). In light of growing evidence suggesting that the softening effect of dynamic recrystallization may play a significant role, alongside thermal softening, in the process of shear band formation and growth, a simple dynamic recrystallization model is proposed and cast within the context of the MTS model with the aid of the aforementioned internal state variable. An initiation criterion for shear localization in rate and temperature-sensitive materials is introduced and used in the present context of high-rate loading, where material rate-dependence is pronounced and substantial temperature increases are achieved due to the dissipative nature of viscoplastic processes. In addition, explicit time integration is adopted to facilitate treatment of the dynamic problems under consideration, where strain rates in excess of 10 4 s –1 are typically attained. Two series of experiments are conducted on AISI 316L stainless steel, employing the commonly used top-hat sample geometry and the Split-Hopkinson Pressure Bar dynamic test system. Axi-symmetric finite element simulation results are compared to cross-sectional micrographs of recovered samples and experimental load–displacement results, in order to examine the performance of the proposed framework and demonstrate its effectiveness in treating the initiation and growth of adiabatic shear banding in dynamically loaded metallic materials. These comparisons demonstrate that thermal softening alone is insufficient to induce shear localization behaviors observed in some materials, such as stainless steel, and support the hypothesis that dynamic recrystallization and/or other softening mechanisms play an essential role in this process.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Dynamic flow stress of pure polycrystalline aluminum: Pressure-shear plate impact experiments and extension of dislocation-based modeling to large strains

The dynamic thermo-mechanical behavior of pure aluminum has attracted renewed interest lately due to experimental observations of an anomalous increase in Hugoniot Elastic Limit (HEL) at incipient plasticity and elevated temperatures in polycrystalline pure metals. In context of current dislocation-mediated plasticity models for metals, this increase in dynamic strength is indicative of a transition in the rate controlling mechanism for dislocation glide from being thermally assisted to phonon-drag restricted due to increase in phonon viscosity at elevated temperatures. Though these studies have helped to shed light on these important mechanisms operative in FCC metals at incipient plasticity, the extent to which they contribute to flow stress, particularly at larger strains, remains unclear. Here, we address these questions through a combined experimental and modeling effort focused on investigating the evolution of dynamic flow stress in polycrystalline aluminum using experimental data gathered from a series of combined pressure-and-shear plate impact (PSPI) experiments designed to reveal the flow stress of pure aluminum at strain rates ~ 10 5 /s, plastic strains of up to 40% and temperatures ranging from room to 866 K. In all cases, the flow stress of aluminum, as inferred from the measured transverse particle velocity histories at the free surface of an elastic tungsten carbide target plate, reveals saturation with increasing plastic strains at stress levels that decrease with increasing test temperatures. Numerical simulations are performed to correlate the experimentally observed temperature and strain rate dependence of flow stress at small and large plastic strains using the Austin-McDowell dislocation-mediated plasticity model parametrized to normal plate impact experiments conducted in an earlier study by Zaretsky and Kanel (2012). Extensions to the model are made to better represent dynamic behavior of pure aluminum at larger plastic strains as observed in elevated temperature split Hopkinson Pressure bar (SPHB) experiments of Samanta (1971) and Lindholm and Yeakly (1965), and the combined pressure-and-shear plate-impact experiments conducted in the present study. The main theoretical extension to the Austin-McDowell model made in this paper is the introduction of a new rate- and temperature- dependent dynamic recovery function, which can potentially allow for an effective reduction in the rate of accumulation of dislocations at large plastic strains. The numerical predictions of the revised and re-calibrated plasticity model are brought into agreement with the experimental observations, correlating sufficiently well with dynamic yield stress at incipient plasticity and the flow stress levels at larger plastic strains, plastic strain rates in the range 10 3 – 10 6 /s, and elevated temperatures up to near melt. The model, in concert with the experimental measurements, suggests that at incipient plasticity the rate governing mechanism for plastic flow is phonon-drag restricted dislocation glide, whereas, at higher magnitudes of plastic strain, it transitions to stress-assisted thermally activated glide. The transition between these two rate governing mechanisms is controlled by the evolution of dislocations throughout the deformation process.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Dynamic recrystallization behavior of an as-cast TiAl alloy during hot compression

High temperature compressive deformation behaviors of as-cast Ti–43Al–4Nb–1.4W–0.6B alloy were investigated at temperatures ranging from 1050 °C to 1200 °C, and strain rates from 0.001 s{sup −1} to 1 s{sup −1}. Electron back scattered diffraction technique, scanning electron microscopy and transmission electron microscopy were employed to investigate the microstructural evolutions and nucleation mechanisms of the dynamic recrystallization. The results indicated that the true stress–true strain curves show a dynamic flow softening behavior. The dependence of the peak stress on the deformation temperature and the strain rate can well be expressed by a hyperbolic-sine type equation. The activation energy decreases with increasing the strain. The size of the dynamically recrystallized β grains decreases with increasing the value of the Zener–Hollomon parameter (Z). When the flow stress reaches a steady state, the size of β grains almost remains constant with increasing the deformation strain. The continuous dynamic recrystallization plays a dominant role in the deformation. In order to characterize the evolution of dynamic recrystallization volume fraction, the dynamic recrystallization kinetics was studied by Avrami-type equation. Besides, the role of β phase and the softening mechanism during the hot deformation was also discussed in details. - Highlights: • The size of DRXed β grains decreases with increasing the value of the Z. • The CDRX plays a dominant role in the deformation. • The broken TiB{sub 2} particles can promote the nucleation of DRX.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Self similarities in desalination dynamics and performance using capacitive deionization

Charge transfer and mass transport are two underlying mechanisms which are coupled in desalination dynamics using capacitive deionization (CDI). We developed simple reduced-order models based on a mixed reactor volume principle which capture the coupled dynamics of CDI operation using closed-form semi-analytical and analytical solutions. We use the models to identify and explore self-similarities in the dynamics among flow rate, current, and voltage for CDI cell operation including both charging and discharging cycles. The similarity approach identifies the specific combination of cell (e.g. capacitance, resistance) and operational parameters (e.g. flow rate, current) which determine a unique effluent dynamic response. We here demonstrate self-similarity using a conventional flow between CDI (fbCDI) architecture, and we hypothesize that our similarity approach has potential application to a wide range of designs. We performed an experimental study of these dynamics and used well-controlled experiments of CDI cell operation to validate and explore limits of the model. For experiments, we used a CDI cell with five electrode pairs and a standard flow between (electrodes) architecture. Guided by the model, we performed a series of experiments that demonstrate natural response of the CDI system. We also identify cell parameters and operation conditions which lead to self-similar dynamics under a constant current forcing function and perform a series of experiments by varying flowrate, currents, and voltage thresholds to demonstrate self-similarity. Based on this study, we hypothesize that the average differential electric double layer (EDL) efficiency (a measure of ion adsorption rate to EDL charging rate) is mainly dependent on user-defined voltage thresholds, whereas flow efficiency (measure of how well desalinated water is recovered from inside the cell) depends on cell volumes flowed during charging, which is determined by flowrate, current and voltage thresholds. Results of experiments strongly support this hypothesis. Results show that cycle efficiency and salt removal for a given flowrate and current are maximum when average EDL and flow efficiencies are approximately equal. We further explored a range of CC operations with varying flowrates, currents, and voltage thresholds using our similarity variables to highlight trade-offs among salt removal, energy, and throughput performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Experimental study of the stability and dynamics of a two-dimensional ideal vortex under external strain

The dynamics of two-dimensional (2-D) ideal fluid vortices is studied experimentally in the presence of an irrotational strain flow. Laboratory experiments are conducted using strongly magnetized pure electron plasmas, a technique which is made possible by the isomorphism between the drift–Poisson equations describing plasma dynamics transverse to the field and the 2-D Euler equations describing an ideal fluid. The electron plasma system provides an excellent opportunity to study the dynamics of a 2-D Euler fluid due to weak dissipation and weak 3-D effects, simple diagnosis and precise control. The plasma confinement apparatus used here was designed specifically to study vortex dynamics under the influence of external flow by applying boundary conditions in two dimensions. Additionally, vortex-in-cell simulations are carried out to complement the experimental results and to extend the parameter range of the studies. It is shown that the global dynamics of a quasi-flat vorticity profile is in good quantitative agreement with the theory of a piecewise-constant elliptical patch of vorticity, including the equilibria, dynamical orbits and stability properties. Deviations from the elliptical patch theory are observed for non-flat vorticity profiles; they include inviscid damping of the orbits and modified stability limits. The dependence of these phenomena on the flatness of the initial profile is discussed. The relationship of these results to other theoretical, numerical and experimental studies is also discussed.

Mechanics↗
DOE OSTI2015

Structure and dynamics of GeoCyp: a thermophilic cyclophilin with a novel substrate binding mechanism that functions efficiently at low temperatures

Thermophilic proteins have found extensive use in research and industrial applications due to their high stability and functionality at elevated temperatures while simultaneously providing valuable insight into our understanding of protein folding, stability, dynamics, and function. Cyclophilins, a ubiquitously expressed family of peptidyl-prolyl isomerases with a range of biological functions and disease associations, have been utilized both for conferring stress tolerances and in exploring the link between conformational dynamics and enzymatic function. To date, however, no active thermophilic cyclophilin has been fully biophysically characterized. Here, we determine the structure of a thermophilic cyclophilin (GeoCyp) from Geobacillus kaustophilus, characterize its dynamic motions over several timescales using an array of methodologies that include chemical shift-based methods and relaxation experiments over a range of temperatures, and measure catalytic activity over a range of temperatures in order to compare structure, dynamics, and function to a mesophilic counterpart, human Cyclophilin A (CypA). Unlike most thermophile/mesophile pairs, GeoCyp catalysis is not substantially impaired at low temperatures as compared to CypA, retaining ~70% of the activity of its mesophilic counterpart. Examination of substrate-bound ensembles reveals a mechanism by which the two cyclophilins may have adapted to their environments through altering dynamic loop motions and a critical residue that acts as a clamp to regulate substrate binding differentially in CypA and GeoCyp. Despite subtle differences in conformational movements, dynamics over fast (ps-ns) and slow (μs) timescales are largely conserved between the two proteins.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2016

Onset of Cooperative Dynamics in an Equilibrium Glass-Forming Metallic Liquid

Onset of cooperative dynamics has been observed in many molecular liquids, colloids, and granular materials in the metastable regime on approaching their respective glass or jamming transition points, and is considered to play a significant role in the emergence of the slow dynamics. However, the nature of such dynamical cooperativity remains elusive in multicomponent metallic liquids characterized by complex many-body interactions and high mixing entropy. Herein, we report evidence of onset of cooperative dynamics in an equilibrium glass-forming metallic liquid (LM601: Zr 51 Cu 36 Ni 4 Al 9 ). This is revealed by deviation of the mean effective diffusion coefficient from its high-temperature Arrhenius behavior below T A ≈ 1300 K, i.e., a crossover from uncorrelated dynamics above T A to landscape-influenced correlated dynamics below T A . Moreover, the onset/ crossover temperature T A in such a multicomponent bulk metallic glass-forming liquid is observed at approximately twice of its calorimetric glass transition temperature (T g ≈ 697 K) and in its stable liquid phase, unlike many molecular liquids.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Structural and Rotational Dynamics of Carbon Dioxide in 1-Alkyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquids: The Effect of Chain Length

Ionic liquids (ILs) have been proposed as possible carbon dioxide (CO 2 ) carbon capture media, and so it is useful to understand the dynamics of both the dissolved gas and its IL environment as well as how altering the IL affects these dynamics. With increasing alkyl chain length, it is well established that ILs obtain a mesoscopic structural feature assigned to polarapolar segregation, and the change in structure with chain length affects dynamics. In this work, the dynamics of CO 2 in a series of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids (ILs), where alkyl is ethyl, butyl, hexyl, or decyl, were investigated using ultrafast infrared spectroscopy by measuring the reorientation and spectral diffusion of carbon dioxide in the ILs. It was found that reorientation of the carbon dioxide occurs on 3 timescales, which correspond to 2 different timescales of restricted wobbling-in-a-cone motions and a long time complete diffusive reorientation. The complete reorientation slows with increasing chain length but less than the increases in viscosity of the bulk liquids. Spectral diffusion, measured with 2D IR spectroscopy, is caused by a combination of the liquids’ structural fluctuations and reorientation of the CO 2 . The data were analyzed using recent theory that takes into account both contributions to spectral diffusion and extracts the structural spectral diffusion. Different components of the structural fluctuations have distinct dependences on the alkyl chain length. All of the dynamics are fast compared to the complete orientational randomization of the bulk ILs, as measured with optical heterodyne detected optical Kerr effect measurements. The results indicate a hierarchy of constraint releases in the liquids that give rise to increasingly slower dynamics.

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

Insights into Rotational and Translational Dynamics in Mixtures of Ethylene Glycol and Choline Chloride Using Nuclear Magnetic Resonance Techniques

This work examines molecular dynamics and interactions in ethylene glycol–choline chloride (EG–ChCl) mixtures across 0–33 mol % ChCl, spanning the true eutectic region near 17–20 mol % and the commonly used 1:2 formulation. We combine pulsed-field-gradient (PFG) diffusion, fast-field-cycling (FFC) relaxometry, temperature-dependent 13 C T 1 , and nuclear Overhauser effect spectroscopy (NOESY) to disentangle local from macroscopic dynamics. PFG and FFC show that both translational and average rotational motions largely track the strong increase in viscosity with ChCl content, with ethylene glycol consistently diffusing faster than the choline cation and no global dynamical anomaly at the eutectic composition. More subtle, site-specific composition effects nevertheless emerge. The ratio of the diffusion coefficient of the hydroxyl group of choline to the diffusion coefficient of the methyl group of choline displays a shallow minimum in the 17–25 mol % region, indicating a modest change in how the hydroxyl-bearing end of choline samples the underlying translational motion relative to the methyl groups. 13 C T 1 analysis shows that rotational correlation times at 25 °C generally increase with ChCl, reflecting viscosity-coupled slowing, while the CH 2 –N α site exhibits a small but reproducible deviation from this monotonic trend near the eutectic. NOESY spectra at similar compositions reveal enhanced cross-relaxation between EG and choline protons, consistent with increased headgroup–solvent contact density rather than a wholesale structural rearrangement. Overall, our multitechnique study demonstrates that EG–ChCl dynamics are predominantly viscosity-dominated, with the eutectic region acting as a subtle dynamical crossover where specific choline segments become maximally coupled to the hydrogen-bond network. These insights refine the structure–dynamics picture of choline-chloride DESs and provide practical guidance for tuning composition in electrochemical, separation, and catalytic applications.

diffusion↗