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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Toward Molecule-Specific Geochemistry of Heavy Ends: Application to the Upstream Oil Industry

Detailed molecular analysis of the composition of petroleum is typically performed on only the light (volatile) fraction, using analyses involving gas chromatography (GC). Heavier (nonvolatile) components such as kerogen, bitumen, and asphaltenes, which are relevant to conventional reservoirs and particularly to unconventional gas shale and tight oil formations, are not amenable to analysis by GC and instead are typically studied by more phenomenological techniques. This report describes a suite of analytical techniques that can provide sufficient average molecular information on the heavy ends (defined as the nonvolatile fraction) to be useful for a variety of industrial applications, expanding the discipline of molecule-specific geochemistry into the non-GC amenable fractions of petroleum materials. Heavy ends are composed of the elements C, H, N, S, and O, and the bonding environments of each can be measured by various solid state spectroscopies: nuclear magnetic resonance (NMR) and infrared (IR) spectroscopies for C, H, and O; X-ray absorption near-edge structure (XANES) spectroscopy for S and N. Additionally, advances in mass spectrometry, including techniques such as laser desorption laser ionization mass spectrometry (L2MS), can be used to measure the molecular weight and dominant molecular architecture of asphaltenes. Moreover, higher-order structures can be measured: samples of kerogen with representative pore geometry can be prepared, and those pore systems are analyzed with techniques such as X-ray diffraction and neutron scattering. Colloidal structures of asphaltenes can be measured with a variety of techniques, which reveal a hierarchical aggregation structure. These analyses provide sufficient structural data to enable structure–property and structure–function relationships to be determined, which can be applied to the characterization of conventional and unconventional resources. In gas shale and tight oil formations, which contain abundant inorganic minerals as well as kerogen, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is used for simultaneous analysis of mineralogy, kerogen content, and maturity, typically performed at the wellsite. In conventional reservoirs, spatial variations in the asphaltene concentration measured by downhole fluid analysis logging tools are being interpreted with a recently developed equation of state to address upstream issues such as reservoir connectivity, tar mat formation, and fault block migration. Furthermore, as more heavy end analyses are developed, further scientific knowledge and industrial applications of heavy end geochemistry are anticipated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Perpendicular dynamics of runaway electrons in tokamak plasmas

In this paper, it will be shown that the runaway phenomenon in tokamak plasmas cannot be reduced to a one-dimensional problem, based on the competence between electric field acceleration and collisional friction losses in the parallel direction. A Langevin approach, including collisional diffusion in velocity space, will be used to analyze the two-dimensional runaway electron dynamics. An investigation of the runaway probability in velocity space will yield a criterion for runaway, which will be shown to be consistent with the results provided by the more simple test particle description of the runaway dynamics [Fuchs et al., Phys. Fluids 29, 2931 (1986)]. Electron perpendicular collisional scattering will be found to play an important role, relaxing the conditions for runaway. Moreover, electron pitch angle scattering perpendicularly broadens the runaway distribution function, increasing the electron population in the runaway plateau region in comparison with what it should be expected from electron acceleration in the parallel direction only. The perpendicular broadening of the runaway distribution function, its dependence on the plasma parameters, and the resulting enhancement of the runaway production rate will be discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

A Public-Private-Acadmic Partnership to Advance Solar Power Forecasting

The National Center for Atmospheric Research (NCAR) is pleased to have led a partnership to advance the state-of-the-science of solar power forecasting by designing, developing, building, deploying, testing, and assessing the SunCast™ Solar Power Forecasting System. The project has included cutting edge research, testing in several geographically- and climatologically-diverse high penetration solar utilities and Independent System Operators (ISOs), and wide dissemination of the research results to raise the bar on solar power forecasting technology. The partners include three other national laboratories, six universities, and industry partners. This public-private-academic team has worked in concert to perform use-inspired research to advance solar power forecasting through cutting-edge research to advance both the necessary forecasting technologies and the metrics for evaluating them. The project has culminated in a year-long, full-scale demonstration of provide irradiance and power forecasts to utilities and ISOs to use in their operations. The project focused on providing elements of a value chain, beginning with the weather that causes a deviation from clear sky irradiance and progresses through monitoring and observations, modeling, forecasting, dissemination and communication of the forecasts, interpretation of the forecast, and through decision-making, which produces outcomes that have an economic value. The system has been evaluated using metrics developed specifically for this project, which has provided rich information on model and system performance. Research was accomplished on the very short range (0-6 hours) Nowcasting system as well as on the longer term (6-72 hour) forecasting system. The shortest range forecasts are based on observations in the field. The shortest range system, built by Brookhaven National Laboratory (BNL) and based on Total Sky Imagers (TSIs) is TSICast, which operates on the shortest time scale with a latency of only a few minutes and forecasts that currently go out to about 15 min. This project has facilitated research in improving the hardware and software so that the new high definition cameras deployed at multiple nearby locations allow discernment of the clouds at varying levels and advection according to the winds observed at those levels. Improvements over “smart persistence” are about 29% for even these very short forecasts. StatCast is based on pyranometer data measured at the site as well as concurrent meteorological observations and forecasts. StatCast is based on regime-dependent artificial intelligence forecasting techniques and has been shown to improve on “smart persistence” forecasts by 15-50%. A second category of short-range forecasting systems employ satellite imagery and use that information to discern clouds and their motion, allowing them to project the clouds, and the resulting blockage of irradiance, in time. CIRACast (the system produced by the Cooperative Institute for Atmospheric Research [CIRA] at Colorado State University) was already one of the more advanced cloud motion systems, which is the reason that team was brought to this project. During the project timeframe, the CIRA team was able to advance cloud shadowing, parallax removal, and implementation of better advecting winds at different altitudes. CIRACast shows generally a 25-40% improvement over Smart Persistence between sunrise and approximately 1600 UTC (Coordinated Universal Time) . A second satellite-based system, MADCast (Multi-sensor Advective Diffusive foreCast system), assimilates data from multiple satellite imagers and profilers to assimilate a fully three-dimensional picture of the cloud into the dynamic core of WRF. During 2015, MADCast (provided at least 70% improvement over Smart Persistence, with most of that skill being derived during partly cloudy conditions. That allows advection of the clouds via the Weather Research and Forecasting (WRF) model dynamics directly. After WRF-Solar™ showed initial success, it was also deployed in nowcasting mode with coarser runs out to 6 hours made hourly. It provided improvements on the order of 50-60% over Smart Persistence for forecasts up to 1600 UTC. The advantages of WRF-Solar-Nowcasting and MADCast were then blended to develop the new MAD-WRF model that incorporates the most important features of each of those models, both assimilating satellite cloud fields and using WRF-So far physics to develop and dissipate clouds. MAE improvements for MAD-WRF for forecasts from 3-6 hours are improved over WRF-Solar-Now by 20%. While all the Nowcasting system components by themselves provide improvement over Smart Persistence, the largest benefit is derived when they are smartly blended together by the Nowcasting Integrator to produce an integrated forecast. The development of WRF-Solar™ under this project has provided the first numerical weather prediction (NWP) model specifically designed to meet the needs of irradiance forecasting. The first augmentation improved the solar tracking algorithm to account for deviations associated with the eccentricity of the Earth’s orbit and the obliquity of the Earth. Second, WRF-Solar™ added the direct normal irradiance (DNI) and diffuse (DIF) components from the radiation parameterization to the model output. Third, efficient parameterizations were implemented to either interpolate the irradiance in between calls to the expensive radiative transfer parameterization, or to use a fast radiative transfer code that avoids computing three-dimensional heating rates but provides the surface irradiance. Fourth, a new parameterization was developed to improve the representation of absorption and scattering of radiation by aerosols (aerosol direct effect). A fifth advance is that the aerosols now interact with the cloud microphysics, altering the cloud evolution and radiative properties, an effect that has been traditionally only implemented in atmospheric computationally costly chemistry models. A sixth development accounts for the feedbacks that sub-grid scale clouds produce in shortwave irradiance as implemented in a shallow cumulus parameterization Finally, WRF-Solar™ also allows assimilation of infrared irradiances from satellites to determine the three dimensional cloud field, allowing for an improved initialization of the cloud field that increases the performance of short-range forecasts. We find that WRF-Solar™ can improve clear sky irradiance prediction by 15-80% over a standard version of WRF, depending on location and cloud conditions. In a formal comparison to the NAM baseline, WRF-Solar™ showed improvements in the Day-Ahead forecast of 22-42%. The SunCast™ system requires substantial software engineering to blend all of the new model components as well as existing publically available NWP model runs. To do this we use an expert system for the Nowcasting blender and the Dynamic Integrated foreCast (DICast®) system for the NWP models. These two systems are then blended, we use an empirical power conversion method to convert the irradiance predictions to power, then apply an analog ensemble (AnEn) approach to further tune the forecast as well as to estimate its uncertainty. The AnEn module decreased RMSE (root mean squared error) by 17% over the blended SunCast™ power forecasts and provided skill in the probabilistic forecast with a Brier Skill Score of 0.55. In addition, we have also developed a Gridded Atmospheric Forecast System (GRAFS) in parallel, leveraging cost share funds. An economic evaluation based on Production Cost Modeling in the Public Service Company of Colorado showed that the observed 50% improvement in forecast accuracy will save their customers $819,200 with the projected MW deployment for 2024. Using econometrics, NCAR has scaled this savings to a national level and shown that an annual expected savings for this 50% forecast error reduction ranges from $11M in 2015 to $43M expected in 2040 with increased solar deployment. This amounts to a $455M discounted savings over the 26 year period of analysis.

14 SOLAR ENERGY↗
DOE OSTI2026

Formation of Non-Doped Cubic Lithium Lanthanum Zirconium Oxide Nanofibers: Insights from In Situ Synchrotron X-Ray Scattering

This study investigates the formation mechanism of non-doped cubic lithium lanthanum zirconium oxide (c-LLZO) nanofibers using in situ synchrotron X-ray scattering techniques. Electrospun polymer precursor nanofibers were annealed at temperatures up to 800 °C, enabling real-time tracking of phase transitions via simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and evolved CO 2 gas analysis. The results reveal a three-step transformation pathway: polymer decomposition, formation of La 2 Zr 2 O 7 (LZO), and direct conversion of LZO to c-LLZO without intermediate tetragonal phases detected within the sensitivity of our in situ WAXS measurement. Cryo-electron energy loss spectroscopy (EELS) further elucidates the role of lithium diffusion, showing Li enrichment at fiber surfaces and Li deficiency in the interior, which stabilizes the cubic phase. This Li segregation effect in nanostructured LLZO materials extends beyond the previously reported size effect. This work advances the understanding of c-LLZO formation mechanisms and provides practical insights for optimizing synthesis routes to achieve phase-pure c-LLZO for solid-state battery applications.

LLZO phase stability↗
DOE OSTI2016

Quasielastic neutron scattering with in situ humidity control: Water dynamics in uranyl fluoride

The structural phase diagram of uranyl fluoride (UO{sub 2}F{sub 2}), while incomplete, contains at least one anhydrous crystal structure and a second, zeolite-like structure with the formula [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} that can be produced by adding water to the anhydrous structure. While traditional diffraction measurements can easily differentiate these crystals, additional aqueous structures (in general of the form UO{sub 2}F{sub 2} + xH{sub 2}O) have been proposed as well. We present results using a novel sample environment setup to intercalate water during a quasielastic neutron scattering measurement over the course of 86 h. Our sample environment allows low-pressure (<2 atm) humid air flow across the sample coupled with a system to control the relative humidity of this air flow between 10% and 70%. The water dynamics in UO{sub 2}F{sub 2} and [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4} are sufficiently different to distinguish them, with water in the latter executing a restricted diffusion (D = 2.7 × 10{sup −6} cm{sup 2}/s) within the structure's accessible pores (r = 3.17 Å) such that the dynamics can be used as a fingerprinting tool. We confirm that water vapor pressure is the driving thermodynamic force for the conversion of the anhydrous structure to [(UO{sub 2}F{sub 2})(H{sub 2}O)]{sub 7} ⋅ (H{sub 2}O){sub 4}, and we demonstrate the feasibility of extending this approach to aqueous forms of UO{sub 2}F{sub 2} + xH{sub 2}O. This method has general applicability to systems in which water content itself is a driving variable for structural or dynamical phase transitions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Superior thermoelectric performance in PbTe-PbS pseudo-binary. Extremely low thermal conductivity and modulated carrier concentration

Lead chalcogenides have exhibited their irreplaceable role as thermoelectric materials at the medium temperature range, owing to highly degenerate electronic bands and intrinsically low thermal conductivities. PbTe-PbS pseudo-binary has been paid extensive attentions due to the even lower thermal conductivity which originates largely from the coexistence of both alloying and phase-separated precipitations. To investigate the competition between alloying and phase separation and its pronounced effect on the thermoelectric performance in PbTe-PbS, we systematically studied Spark Plasma Sintered (SPSed), 3 at% Na- doped (PbTe) 1-x (PbS)x samples with x=10%, 15%, 20%, 25%, 30% and 35% by means of transmission electron microscopy (TEM) observations and theoretical calculations. Corresponding to the lowest lattice thermal conductivity as a result of the balance between point defect- and precipitates- scattering, the highest figure of merit ZT~2.3 was obtained at 923 K when PbS phase fraction x is at 20%. The consistently lower lattice thermal conductivities in SPSed samples compared with corresponding ingots, resulting from the powdering and follow-up consolidation processes, also contribute to the observed superior ZT. Notably, the onset of carrier concentration modulation ~600 K due to excessive Na’s diffusion and re-dissolution leads to the observed saturations of electrical transport properties, which is believed equally crucial to the outstanding thermoelectric performance of SPSed PbTe-PbS samples.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Water dynamics in hydrated amorphous materials: a molecular dynamics study of the effects of dehydration in amorphous calcium carbonate

Amorphous calcium carbonate (ACC) is often a critical transient phase in the formation of crystalline phases of CaCO 3 via dehydration of hydrated ACC. The behavior of the water molecules plays a pivotal role in this transformation. We report here the dynamics of water molecules in ACC at hydration levels from CaCO 3 ·1H 2 O to CaCO 3 ·0.25H 2 O using molecular dynamics (MD) simulations. Due to the presence of highly hydrophilic Ca 2+ and the strong H-bond acceptor CO 3 2- , most of the water molecules in our simulations have restricted translational and orientational dynamics. These are referred here as ‘slow water’. However, a small fraction of them show high diffusivity at all hydration states and are referred here as ‘fast water’. The computed diffusion coefficients of the slow waters, as extrapolated from simulation results, yield diffusion distances of the order of μm on the 1 hour time scale, consistent with rapid dehydration of ACC nano-particles in the laboratory. We correlate our fast waters with the water molecules in the percolating water-rich, Ca 2+ -deficient nano-pores in the structure of Goodwin et al. [Chem. Mater., 2010, 22, 3197], obtained by analysis of X-ray scattering data, and our slow waters with those in the Ca 2+ -rich volumes with less water in their model. The fast waters can be considered to be free rotors on the ns time scale and have orders of magnitude shorter rotational relaxation times than the slow waters.

Saharay, Moumita↗
DOE OSTI2014

The CO-to-H{sub 2} conversion factor across the Perseus molecular cloud

We derive the CO-to-H{sub 2} conversion factor, X {sub CO} = N(H{sub 2})/I {sub CO}, across the Perseus molecular cloud on sub-parsec scales by combining the dust-based N(H{sub 2}) data with the I {sub CO} data from the COMPLETE Survey. We estimate an average X {sub CO} ∼ 3 × 10{sup 19} cm{sup –2} K{sup –1} km{sup –1} s and find a factor of ∼3 variations in X {sub CO} between the five sub-regions in Perseus. Within the individual regions, X {sub CO} varies by a factor of ∼100, suggesting that X {sub CO} strongly depends on local conditions in the interstellar medium. We find that X {sub CO} sharply decreases at A{sub V} ≲ 3 mag but gradually increases at A{sub V} ≳ 3 mag, with the transition occurring at A{sub V} where I {sub CO} becomes optically thick. We compare the N(H I), N(H{sub 2}), I {sub CO}, and X {sub CO} distributions with two models of the formation of molecular gas, a one-dimensional photodissociation region (PDR) model and a three-dimensional magnetohydrodynamic (MHD) model, tracking both the dynamical and chemical evolution of gas. The PDR model based on the steady state and equilibrium chemistry reproduces our data very well but requires a diffuse halo to match the observed N(H I) and I {sub CO} distributions. The MHD model matches our data reasonably well, suggesting that time-dependent effects on H{sub 2} and CO formation are insignificant for an evolved molecular cloud like Perseus. However, we find interesting discrepancies, including a broader range of N(H I), likely underestimated I {sub CO}, and a large scatter of I {sub CO} at small A{sub V} . These discrepancies most likely result from strong compressions and rarefactions and density fluctuations in the MHD model.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Response of Surface Ultraviolet and Visible Radiation to Stratospheric SO 2 Injections

Climate modification by stratospheric SO 2 injections, to form sulfate aerosols, may alter the spectral and angular distributions of the solar ultraviolet and visible radiation that reach the Earth’s surface, with potential consequences to environmental photobiology and photochemistry. We used modeling results from the CESM1(WACCM) stratospheric aerosol geoengineering large ensemble (GLENS) project, following the RCP8.5 emission scenario, and one geoengineering experiment with SO 2 injections in the stratosphere, designed to keep surface temperatures at 2020 levels. Zonally and monthly averaged vertical profiles of O 3 , SO 2 , and sulfate aerosols, at 30 N and 70 N, served as input into a radiative transfer model, to compute biologically active irradiances for DNA damage ( i DNA ), UV index (UVI), photosynthetically active radiation (PAR), and two key tropospheric photodissociation coefficients ( j O1D for O 3 + hν (λ < 330 nm) → O( 1 D) + O 2 ; and j NO2 for NO 2 + hν (λ < 420 nm) → O( 3 P) + NO). We show that the geoengineering scenario is accompanied by substantial reductions in UV radiation. For example, comparing March 2080 to March 2020, i DNA decreased by 25% to 29% in the subtropics (30 N) and by 26% to 33% in the polar regions (70 N); UVI decreased by 19% to 20% at 30 N and 23% to 26% at 70 N; and j O1D decreased by 22% to 24% at 30 N and 35% to 40% at 70 N, with comparable contributions from sulfate scattering and stratospheric O 3 recovery. Different responses were found for processes that depend on longer UV and visible wavelengths, as these are minimally affected by ozone; PAR and j NO2 were only slightly lower (9–12%) at 30 N, but much lower at 70 N (35–40%). Similar reductions were estimated for other months (June, September, and December). Large increases in the PAR diffuse-direct ratio occurred in agreement with previous studies. Absorption by SO 2 gas had a small (~1%) effect on j O1D , i DNA , and UVI, and no effect on j NO2 and PAR.

42 ENGINEERING↗
DOE OSTI2022

Tracking structural solvent reorganization and recombination dynamics following e – photoabstraction from aqueous I – with femtosecond x-ray spectroscopy and scattering

Here we present a sub-picosecond resolved investigation of the structural solvent reorganization and geminate recombination dynamics following 400 nm two-photon excitation and photodetachment of a valence p electron from the aqueous atomic solute, I–(aq). The measurements utilized time-resolved X-ray Absorption Near Edge Structure (TR-XANES) spectroscopy and X-ray Solution Scattering (TR-XSS) at the Linac Coherent Light Source x-ray free electron laser in a laser pump/x-ray probe experiment. The XANES measurements around the L 1 -edge of the generated nascent iodine atoms (I 0 ) yield an average electron ejection distance from the iodine parent of 7.4 ± 1.5 Å with an excitation yield of about 1/3 of the 0.1M NaI aqueous solution. The kinetic traces of the XANES measurement are in agreement with a purely diffusion-driven geminate iodine–electron recombination model without the need for a long-lived (I 0 :e–) contact pair. Nonequilibrium classical molecular dynamics simulations indicate a delayed response of the caging H 2 O solvent shell and this is supported by the structural analysis of the XSS data: We identify a two-step process exhibiting a 0.1 ps delayed solvent shell reorganization time within the tight H-bond network and a 0.3 ps time constant for the mean iodine–oxygen distance changes. The results indicate that most of the reorganization can be explained classically by a transition from a hydrophilic cavity with a well-ordered first solvation shell (hydrogens pointing toward I–) to an expanded cavity around I 0 with a more random orientation of the H 2 O molecules in a broadened first solvation shell.

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

Solvation Structure and Dynamics of Mg(TFSI) 2 Aqueous Electrolyte

Using ab initio molecular dynamics (AIMD) simulations, classical molecular dynamics (CMD) simulations, small-angle X-ray scattering (SAXS), and pulsed-field gradient nuclear magnetic resonance (PFG-NMR), the solvation structure and ion dynamics of magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2 ) aqueous electrolyte at 1, 2, and 3 m concentrations are investigated. From AIMD and CMD simulations, the first solvation shell of an Mg 2+ ion is found to be composed of six water molecules in an octahedral configuration and the solvation shell is rather rigid. The TFSI - ions prefer to stay in the second solvation shell and beyond. Meanwhile, the comparable diffusion coefficients of positive and negative ions in Mg(TFSI) 2 aqueous electrolytes have been observed, which is mainly due to the formation of the stable [Mg(H 2 O) 6 ] 2+ complex, and, as a result, the increased effective Mg ion size. Finally, the calculated correlated transference numbers are lower than the uncorrelated ones even at the low concentration of 2 and 3 m, suggesting the enhanced correlations between ions in the multivalent electrolytes. This work provides a molecular-level understanding of how the solvation structure and multivalency of the ion affect the dynamics and transport properties of the multivalent electrolyte, providing insight for rational designs of electrolytes for improved ion transport properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Gramicidin and chlorhexidine encapsulated in bicontinuous microemulsions: Antimicrobial activity performance and their impact on self‐assembly

The utility of bicontinuous microemulsions (BMEs) as carriers of the antimicrobial peptide (AMP) gramicidin D and antiseptic chlorhexidine was investigated for possible topical delivery to chronic wounds. The two water-insoluble solutes dissolved in pre-formed one-phase BMEs of Water/Polysorbate 80/Limonene/Ethanol/Glycerol and Water/Aerosol-OT (AOT)/Polysorbate 85/Isopropyl Myristate and an AOT/Polysorbate 85 Winsor-III system, achieving gramicidin and chlorhexidine concentrations of 1.0 wt% and 0.5% individually and 0.5% and 0.3% in mixtures at 22°C, respectively. Small-angle neutron scattering measurements demonstrated that both solutes decreased surfactant interfacial activity and increased interfacial fluidity for the Polysorbate 80 system. For the AOT/Polysorbate 85 systems, ellipsoidal aggregates consisting of gramicidin and likely adsorbed surfactant and oil formed, while chlorhexidine enhanced the surface activity of surfactants. According to bioassays performed on artificial skin, the incorporation of melittin, gramicidin, and chlorhexidine in general enhanced the bioactivity of Polysorbate 80 BMEs for 24 h treatment against relevant antibiotic-resistant bacteria found on skin relative to controls. Yet, BME treatments were less effective than aqueous melittin control, in contrast to well diffusion bioassays performed previously. The results reflect the strong impact of AMPs and antiseptics on BME structure and dynamics and the complexity of formulating BMEs for optimal antimicrobial activity.

antimicrobial peptides↗
DOE OSTI2014

Extending plasma transport theory to strong coupling through the concept of an effective interaction potential

A method for extending traditional plasma transport theories into the strong coupling regime is presented. Like traditional theories, this is based on a binary scattering approximation, but where physics associated with many body correlations is included through the use of an effective interaction potential. The latter is simply related to the pair-distribution function. Modeling many body effects in this manner can extend traditional plasma theory to orders of magnitude stronger coupling. Theoretical predictions are tested against molecular dynamics simulations for electron-ion temperature relaxation as well as diffusion in one component systems. Emphasis is placed on the connection with traditional plasma theory, where it is stressed that the effective potential concept has precedence through the manner in which screening is imposed. The extension to strong coupling requires accounting for correlations in addition to screening. Limitations of this approach in the presence of strong caging are also discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Resistivity bound for hydrodynamic bad metals

Significance In conventional metals, momentum-relaxing scattering determines the electrical resistivity. In contrast, the resistivity of many strongly correlated metals, across multiple portions of their phase diagrams, is controlled by the electronic mean free path for momentum-conserving interactions ρ ∝ 1 / ℓ ee . We propose that this universality arises in a hydrodynamic limit, where ℓ ee is short. In this limit, we prove that the resistivity can be bounded by incoherent diffusion constants associated with momentum-conserving collisions. In the presence of a nonthermal incoherent diffusive mode—such as an imbalance mode for the charge in different Fermi bands—we find that saturation of our diffusion-limited transport bound implies ρ ∝ 1 / ℓ ee , as observed in experiments.

Lucas, Andrew↗
DOE OSTI2016

Precise determination of water exchanges on a mineral surface

Solvent exchanges on solid surfaces and dissolved ions are a fundamental property important for understanding chemical reactions, but the rates of fast exchanges are poorly constrained. In this paper, we probed the diffusional motions of water adsorbed onto nanoparticles of the mineral barite (BaSO 4 ) using quasi-elastic neutron scattering (QENS) and classical molecular dynamics (MD) to reveal the complex dynamics of water exchange along mineral surfaces. QENS data as a function of temperature and momentum transfer (Q) were fit using scattering functions derived from MD trajectories. The simulations reproduce the dynamics measured in the experiments at ambient temperatures, but as temperature is lowered the simulations overestimate slower motions. Decomposition of the MD-computed QENS intensity into contributions from adsorbed and unbound water shows that the majority of the signal arises from adsorbed species, although the dynamics of unbound water cannot be dismissed. The mean residence times of water on each of the four surface sites present on the barite {001} were calculated using MD: at room temperature the low barium site is 194 ps, whereas the high barium site contains two distributions of motions at 84 and 2.5 ps. These contrast to 13 ps residence time on both sulfate sites, with an additional surface diffusion exchange of 66 ps. Surface exchanges are similar to those of the aqueous ions calculated using the same force field: Ba aq 2+ is 208 ps and SO 4aq 2- is 5.8 ps. Finally, this work demonstrates how MD can be a reliable method to deconvolute solvent exchange reactions when quantitatively validated by QENS measurements.

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

Strategies for Post-Synthetic Functionalization of Mesoporous Carbon Nanomaterial Surfaces

Most widely used carbon-based materials feature a bulk framework tolerant of extreme pH and temperature conditions while maintaining physical robustness, electrical conductivity, and biological relevance due to its inherent nontoxicity. At the nanoscale, the study of porous carbons has been of interest because of the enhanced accessible surface area relative to nonporous analogues. The evolution of synthetic techniques has developed structural allotropes with tunable internal pore diameter averages spanning from sub-nanometer to micron-plus sizes. Within the mesopore range, surface chemical phenomena abide by a kinetic-limited ruleset (ignoring the effects of bulk diffusion, as they do not pertain to this size regime). Further, mesopores provide sufficient volume and surface area for hosting guest species, including metal nanoparticles (MNP), polymers, small organics, and enzymes. These two unique features of mesoporous carbon (MC) drive interest in surface modifications to create new physicochemical functionality to these systems and their hosted species. As a result, the evolution of surface modification techniques has been scattered to disparate niches across the literature. This review compiles the array of elegant methods by which these carbon systems are topically engineered.

functionalization↗