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At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Competition and cooperation: The plasticity of bacterial interactions across environments

Bacteria live in diverse communities, forming complex networks of interacting species. A central question in bacterial ecology is whether species engage in cooperative or competitive interactions. But this question often neglects the role of the environment. Here, we use genome-scale metabolic networks from two different open-access collections (AGORA and CarveMe) to assess pairwise interactions of different microbes in varying environmental conditions (provision of different environmental compounds). By computationally simulating thousands of environments for 10,000 pairs of bacteria from each collection, we found that most pairs were able to both compete and cooperate depending on the availability of environmental resources. This modeling approach allowed us to determine commonalities between environments that could facilitate the potential for cooperation or competition between a pair of species. Namely, cooperative interactions, especially obligate, were most common in less diverse environments. Further, as compounds were removed from the environment, we found interactions tended to degrade towards obligacy. However, we also found that on average at least one compound could be removed from an environment to switch the interaction from competition to facultative cooperation or vice versa. Together our approach indicates a high degree of plasticity in microbial interactions in response to the availability of environmental resources.

Biochemistry & Molecular Biology↗
DOE OSTI2024

Identifying Hydropower Operational Flexibilities in Presence of Streamflow and Net-load Uncertainty (Final Technical report)

In the existing operations, hydropower contributions to future system flexibility are generally modeled while maintaining traditional operating rules and constraints in supporting grid operation, such as the balancing of variable renewable energy production. Moreover, operation of large scale hydropower systems on major rivers has been investigated for decades, utilizing various systems engineering approaches, with the evolving electric grid, as the result of renewable resources integration, compounded by the changing climate (variability of river flows, intensification of hydrologic cycle resulting in more frequent extreme events) affecting water availability, the need for more advanced stochastic modeling and effective uncertainty analysis approaches have become necessary. The research results supported by this funding and presented in this report provide a new look at hydropower operational flexibility enforced by the changes identified above. Understanding how hydropower operates in response to the underlying uncertainties with respect to the system constraints is crucial in identifying its operational flexibility potentials. In this project, the flexibility of the operating hydropower facility is described by capturing uncertainties in both water and power system and formulating the operations as a multistage stochastic optimization problem. The proposed approach supports short- to seasonal-term operations and planning decision horizons.

13 HYDRO ENERGY↗
NASA NTRS2019

Mid-21st Century Ozone Air Quality and Health Burden in China Under Emissions Scenarios and Climate Change

Despite modest emissions reductions of air pollutants in recent years, China still suffers from poor air quality, and the outlook for future air quality in China is uncertain. We explore the impact of two disparate 2050 emissions scenarios relative to 2015 in the context of a changing climate with the Geophysical Fluid Dynamics Laboratory Atmospheric Model version 3 (GFDL-AM3) chemistry-climate model. We impose the same near-term climate change for both emission scenarios by setting global sea surface temperature (SST) and sea ice cover (SIC) to the average over 2010–2019 and 2046–2055, respectively, from a three-member ensemble of GFDL coupled climate model simulations under the RCP8.5 (Representative Concentration Pathway) scenario. By the 2050s, annual mean surface ozone increases throughout China by up to 8 ppbv from climate change alone (estimated by holding air pollutants at 2015 levels while setting SIC and SST to 2050 conditions in the model) and by 8–12 ppbv in a scenario in which emissions of ozone precursors nitrogen oxides (NO (sub x) ) and anthropogenic volatile organic compounds (VOCs) increase by ~10%. In a scenario in which NO (sub x) and anthropogenic VOC emissions decline by 60%, annual mean surface ozone over China decreases by 16–20 ppbv in the 2050s relative to the 2010s. The ozone increase from climate change alone results in an additional 62 000 premature deaths in China as compared to 330 000 fewer premature deaths by the 2050s under a strong emissions mitigation scenario. In springtime over Southwestern China in the 2050s, the model projects 9–12 ppbv enhancements to surface ozone from the stratosphere (diagnosed with a model tracer) and from international anthropogenic emissions (diagnosed by differencing AM3 simulations with the same emissions within China but higher versus lower emissions in the rest of the world). Our findings highlight the effectiveness of emissions controls in reducing the health burden in China due to air pollution, and also the potential for climate change and rising global emissions to offset, at least partially, some of the ozone decreases attained with regional emission reductions in China.

Westervelt, D. M.↗
DOE OSTI2025

Experimental and modeling study of the autoignition behavior of a saturated heterocycle: Pyrrolidine

Experiments are conducted in both rapid compression machine (RCM) and shock tube (ST) to better quantify autoignition behavior (e.g., ignition delay, heat release) and understand heteroatomic effects in heterocyclic compounds, which are important reference components for the combustion of biomass-derived liquid fuels. These tests focus on the nitrogen-containing, five-membered saturated ring, pyrrolidine, at diluted conditions covering pressures of 20 and 50 bar, temperatures of 720–1450 K and a range of stoichiometries (ϕ = 0.5–2). A chemical kinetic model is developed and coupled to an existing combustion kinetics framework describing key nitrogen containing intermediates (e.g. pyrrole, ammonia and NOx). H-abstraction reactions by OH, H, CH 3 and HO 2 , are determined using ab-initio transition state theory methods, while analogies to cyclopentane are adopted for many other reactions, such as ring-opening. Here, the autoignition measurements reveal the lack of negative temperature coefficient (NTC) behavior and low-temperature chemistry for pyrrolidine, as opposed to its saturated hydrocarbon analogue, cyclopentane. Interestingly, at the lowest temperatures (T < 750 K), the reactivity of cyclopentane is greater than pyrrolidine, while at higher temperatures, pyrrolidine becomes more reactive. Agreement between the experimental measurements and the model is good, and it is found that H-abstraction reactions by HO 2 and ensuing chemistry play key roles in controlling the reactivity of this cyclic amine. Most of the fluxes, i.e., >70 %, are predicted to move through 1- or 2-pyrroline (C 4 H 7 N) and then the cyclic C 4 H 6 N radical, at both lower and higher temperatures, to form either CH 2 CHCHCHNH via ring-opening or pyrrole via β-scission. It appears that the ring opens more easily at lower temperature whereas the C–H β-scission dominates at higher temperature and lower pressure, such that the reaction of the fuel radical intermediate carrying an unpaired electron on the nitrogen atom with HO 2 is the next most notable in promoting oxidation. When comparing pyrrolidine and cyclopentane, which exhibits distinct pathways in different temperature regimes, the pyrrolidine pathways and sensitivity analysis align more closely to the high temperature case of cyclopentane where the important role of HO 2 radicals is seen to provide chain branching through HO 2 reaction with the fuel, accompanied by H 2 O 2 formation and decomposition to OH. The formation of 5-membered diene rings and ring opening reactions are also found to be highly relevant. Of particular note, it is found that there is little influence of small molecule nitrogen-chemistry, e.g., NH 2 , HCN, NO/NO 2 on the reactivity of the pyrrolidine mixtures investigated here where no recirculated combustion gases are included.

Autoignition↗
NASA NTRS1995

The fate of atmospheric phosgene and the stratospheric chlorine loadings of its parent compounds: CCl4, C2Cl4, C2HCL3, CH3CCl3, and CHCl3

A study of the tropospheric and stratospheric cycles of phosgene is carried out to determine its fate and ultimate role in controlling the ozone depletion potentials of its parent compounds. Tropospheric phosgene is produced from the OH-initiated oxidation of C2Cl4, CH3CCl3, CHCl3, and C2HCl3. Simulations using a two-dimensional model indicate that these processes produce about 90 pptv/yr of tropospheric phosgene with an average concentration of about 18 pptv, in reasonable agreement with observations. We estimate a residence time of about 70 days for tropospheric phosgene, with the vast majority being removed by hydrolysis in cloudwater. Only about 0.4% of the phosgene produced in the troposphere avoids wet removal and is transported to the stratosphere, where its chlorine can be released to participate in the catalytic destruction of ozone. Stratospheric phosgene is produced from the photochemical degradation of CCl4, C2Cl4, CHCl3, and CH3CCl3 and is removed by photolysis and downward transport to the troposphere. Model calculations, in good agreement with observations, indicate that these processes produce a peak stratospheric concentration of about 25-30 pptv at an altitude of about 25 km. In contrast to tropospheric phosgene, stratospheric phosgene is found to have a lifetime against photochemical removal of the order of years. As a result, a significant portion of the phosgene that is produced in the stratosphere is ultimately returned to the troposphere, where it is rapidly removed by clouds. This phenomenon effectively decreases the amount of reactive chlorine injected into the stratosphere and available for ozone depletion from phosgene's parent compounds. A similar phenomenon due to the downward transport of stratospheric COFCl produced from CFC-11 is estimated to cause a 7% decrease in the amount of reactive chlorine injected into the stratosphere from this compound. Our results are potentially sensitive to a variety of parameters, most notably the rate of reaction of phosgene with sulfate aerosols. However, on the basis of the observed vertical distribution of COCl2, we estimate that the reaction of COCl2 with sulfate aerosol most likely has a gamma less than 5 x 10(exp -5) and, as a result, has a negligible impact on the stratospheric chlorine loadings of the phosgene parent compounds.

Kindler, T. P.↗
DOE OSTI2024

Formation kinetics and thermodynamic stability of the Aurivillius compounds in Bi 4 Ti 3 O 12 –BiFeO 3 system

Abstract The Aurivillius compounds in the Bi 2 O 3 –Fe 2 O 3 –TiO 2 system, combining ferroelectric, semiconducting, and ferromagnetic properties, have attracted particular interest. Formation kinetics and thermodynamic stability are the fundamental knowledge needed for modeling and predicting the temporal microstructure and property evolution during materials processing but have not yet been addressed by quantitative experimental measurement. This article focuses on the Bi n +1 Fe n –3 Ti 3 O 3 n +3 Aurivillius compounds on the Bi 4 Ti 3 O 12 –BiFeO 3 tie‐line to elucidate the mechanisms and thermodynamic controls responsible for phase formation of compounds with various perovskite‐like layers. Five high‐purity Aurivillius compounds Bi 4 Ti 3 O 12 , Bi 5 FeTi 3 O 15 , Bi 6 Fe 2 Ti 3 O 18 , Bi 7 Fe 3 Ti 3 O 21 , and Bi 8 Fe 4 Ti 3 O 24 with integer n = 3–7 values were synthesized and their phase transformation properties and enthalpies of formation were studied by X‐ray diffraction in situ, high temperature differential scanning calorimetry, and high temperature oxide melt solution calorimetry. Thermodynamic stability of the compounds decreases with increasing n , and formation kinetics gradually slow down, demonstrating the inherent difficulty to synthesize pure Aurivillius compounds with n larger than 8. This difficulty was confirmed by an impurity phase coexisting with Bi 9 Fe 5 Ti 3 O 27 .

Gong, Weiping↗
DOE OSTI2020

Ignition Delay Measurements of Four Component Model Gasolines Exploring the Impacts of Biofuels and Aromatics

This study explores the impacts of combinations of biofuel (ethanol, isobutanol and 2-methyl furan) and aromatic (toluene) compounds in a four component fuel blend, at fixed research octane number (RON) on ignition delay measured in an advanced fuel ignition delay analyzer (AFIDA 2805). Ignition delay measurements were performed over a range of temperatures from 400 to 725 °C (673 to 998 K) and two chamber pressures of 10 and 20 bar. The four component mixtures are compared to primary reference fuels at RON values of 90 and 100. The ignition delay measurements show that as the aromatic and biofuel concentrations increased, two stage ignition behavior was suppressed, at both initial chamber pressures. But both RON 100 (isooctane) and RON 90 reference fuels showed two stage ignition behavior, as did fuel mixtures with low biofuel and aromatic content. RON 90 fuels showed stronger two stage ignition behavior than RON 100 fuels, as expected. Depending on the type of biofuel in the mixture, the ignition delay at low chamber temperatures could be far greater than for the reference fuels. In particular, for the RON 100 mixtures at either 10 or 20 bar initial chamber pressure, the ignition delay at 400 °C (673 K) for the high level blend of 2-methyl furan and toluene (30 vol% of each) exhibited an ignition delay that was 10 times longer than for neat isooctane. The results show the strong non-linear octane blending response of these three biofuel compounds, especially in concert with the kinetic antagonism that toluene is known to display in mixtures with isooctane. These results have implications for the formulation of biofuel mixtures for spark ignition and advanced compression ignition engines, where this non-linear octane blending response could be exploited to improve knock resistance, or modulate the autoignition process.

2-methyl furan↗
DOE OSTI2020

Effect of Fluorination on Lithium Transport and Short-Range Order in Disordered-Rocksalt-Type Lithium-Ion Battery Cathodes

Fluorine substitution is a critical enabler for improving the cycle life and energy density of disordered rocksalt (DRX) Li-ion battery cathode materials which offer prospects for high energy density cathodes, without the reliance on limited mineral resources. Due to the strong Li–F interaction, fluorine also is expected to modify the short-range cation order in these materials which is critical for Li-ion transport. In this work, density functional theory and Monte Carlo simulations are combined to investigate the impact of Li–F short-range ordering on the formation of Li percolation and diffusion in DRX materials. Additionally, the modeling reveals that F substitution is always beneficial at sufficiently high concentrations and can, surprisingly, even facilitate percolation in compounds without Li excess, giving them the ability to incorporate more transition metal redox capacity and thereby higher energy density. It is found that for F levels below 15%, its effect can be beneficial or disadvantageous depending on the intrinsic short-range order in the unfluorinated oxide, while for high fluorination levels the effects are always beneficial. Using extensive simulations, a map is also presented showing the trade-off between transition-metal capacity, Li-transport, and synthetic accessibility, and two of the more extreme predictions are experimentally confirmed.

25 ENERGY STORAGE↗
DOE OSTI2024

Rejection of low-molecular weight neutral organics is highly sensitive to reverse osmosis system design and operation

A computational model was developed to investigate the significance of system design and operating conditions on the rejection of neutral, low-MW organics by reverse osmosis for potable reuse. Here, the model demonstrated that the decrease in local rejection as net driving pressure decreases is substantially greater for moderately rejected compounds than for highly rejected compounds. At recovery values less than 70%, the local permeate concentration can exceed the pressure vessel feed concentration for moderately rejected compounds. System-level rejection of moderately rejected compounds is likewise substantially more sensitive to operating conditions than highly rejected compounds. The findings highlight a drawback of relying on rejection results from bench-scale testing that operates at low recovery, which invariably has higher rejection than full-scale systems operating at similar pressure. The analysis demonstrates a trade-off in which the low-pressure, high-recovery operation desired for potable reuse systems can be detrimental to the removal of low-MW neutral organics. The removal of low-MW neutral organics can be improved if organics rejection is explicitly evaluated during the design process.

42 ENGINEERING↗
DOE OSTI2025

Source attribution of near-surface ozone pollution in Jiangsu Province of China over 2013–2019

Near-surface ozone (O3) is one of the most severe air pollutants in China, particularly over densely populated Jiangsu Province in the Yangtze River Delta. In this study, an O3 source tagging technique is utilized in a chemistry-climate model to quantify the source contributions of various emission sectors and regions for nitrogen oxides (NOx) and volatile organic compounds (VOCs) to O3 concentrations in Jiangsu Province during 2013–2019. The results show that the near-surface O3 in Jiangsu Province is mainly contributed by surrounding and remote anthropogenic NOx emissions through long-range transport. Local anthropogenic NOx emissions account for only 13 % and 18 % of the annual and summertime mean near-surface O3 in Jiangsu Province, respectively. Anthropogenic NOx emissions from the surface transportation, industry, and energy sectors account for 21 %, 22 % and 20 % of the annual mean near-surface O3 concentration in Jiangsu Province, respectively. Biogenic and anthropogenic VOCs emissions each explains one-third of the annual mean near-surface O3 concentration in Jiangsu, while methane and stratospheric chemical production contribute 21 % and 6 %, respectively. The sources from stratospheric production, aircraft, lightning, and foreign emissions are the primary contributors to O3 in the mid- and high troposphere. During high pollution days in Jiangsu Province, the near-surface O3 concentrations increase with the maximum exceeding 20 ppb, which is attributed to both the enhanced photochemical production and regional transport in favorable meteorological conditions.

ozone pollution↗
DOE OSTI2021

Magnetization distribution in Cu 0.6 Mn 2.4 Ge 2 ferromagnet from polarized and non-polarized neutron powder diffraction aided by density-functional theory calculations

The crystal structure and magnetic properties of Cu 0.6 Mn 2.4 Ge 2 have been re-investigated by a combination of extensive magnetic measurements and neutron scattering experiments, aided by electronic structure calculations. The material is found to be a soft ferromagnet with the ordering temperature T C = 316 K. The magnetocaloric effect evaluated from field-dependent magnetization isotherms is equal to 1.2 J/(kg·K) and 2.5 J/(kg·K) under the maximum applied magnetic field of 2 T and 5 T, respectively. The compound crystallizes in the hexagonal space group P6 3 /mmc. A complex structural disorder necessitated testing of several disorder models against the results of non-polarized and polarized neutron scattering experiments and magnetization measurements. Simulations at the density-functional theory level were also performed to identify the most robust solution that properly described the data observed. The final magnetic structure model reveals non-equal magnetic moments on the Mn1 and Mn2 atoms (2.29(9) µ B and 2.7(1) µ B , respectively) and the presence of vacancies and minor Cu substitution defects in both Mn sites. The work demonstrates how the non-polarized and polarized neutron scattering methods can be combined with electronic structure calculations to establish the microscopic structure of magnetic materials with complex crystallographic disorder.

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

Bulk and surface diffusion of neodymium in alpha-uranium: Ab initio calculations and kinetic Monte Carlo simulations

A fundamental understanding of lanthanide transport in metallic fuels is critical for high fidelity modeling of the fuel-cladding chemical interaction (FCCI) phenomenon, which can lead to the formation of brittle intermetallic compounds and premature failure of the cladding. Here we report a combined ab initio density functional theory (DFT) and kinetic Monte Carlo (KMC) study of the bulk diffusivity of Nd in α-U, fully taking into account the effect of radiation enhanced diffusion. In this work, the vacancy mechanism is considered to be the dominant mechanism for the bulk diffusion of Nd since a Nd interstitial is found to be intrinsically unstable in α-U. The surface diffusivity of a Nd adatom on α-U (001) surface has been further predicted using KMC simulations parameterized by DFT calculations. The present study suggests that Nd transport via the surface diffusion mechanism can be many orders of magnitude faster than bulk diffusion. Furthermore, the results from the present lower length scale study can be used to inform mesoscale phase-field simulations to determine the effective diffusion coefficient of Nd through α-U with a porous microstructure.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Linking the Spin Transition of Ferric Iron in δ‐(Al,Fe)OOH to Water Storage in the Lower Mantle

As the most massive geochemical reservoir, the lower mantle affects the Earth's budget of volatile elements, including hydrogen or H 2 O. The properties of minerals in the lower mantle are further affected by changes in the electronic configurations of iron cations, that is, by spin transitions. The feedback between spin transitions and potential storage of H 2 O in solid hydrous phases in the lower mantle, however, remains unexplored. By combining high‐pressure nuclear resonant inelastic X‐ray scattering and high‐pressure high‐temperature X‐ray diffraction experiments, we constrained the thermal equation of state of δ‐(Al,Fe)OOH, a member of the phase H solid solution. Based on the derived thermal equation of state of δ‐(Al,Fe)OOH and the underlying thermodynamic model, we calculate the excess Gibbs free energy that arises from the spin transition of ferric iron in this compound and evaluate the effect on phase equilibria. The results of our analysis show that the spin transition of ferric iron in phase H may significantly reduce the thermodynamic activity and hence the concentration of H 2 O in a coexisting hydrous melt. As a consequence, nominally anhydrous minerals of the lower mantle may become dehydrated in the presence of phase H. Our analysis further suggests that, under certain conditions, the spin transition may expand the thermal stability of Fe 3+ ‐bearing phase H and create a geochemical link between the storage of H 2 O in phase H and ferric iron in the lower mantle.

Buchen, Johannes [Univ. of Bayreuth (Germany); Cal↗
DOE OSTI2022

Hybrid molecular beam epitaxy of germanium-based oxides

Abstract Germanium-based oxides such as rutile GeO 2 are garnering attention owing to their wide band gaps and the prospects of ambipolar doping for application in high-power devices. Here, we present the use of germanium tetraisopropoxide (GTIP), a metal-organic chemical precursor, as a source of germanium for the demonstration of hybrid molecular beam epitaxy for germanium-containing compounds. We use Sn 1- x Ge x O 2 and SrSn 1- x Ge x O 3 as model systems to demonstrate our synthesis method. A combination of high-resolution X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy confirms the successful growth of epitaxial rutile Sn 1- x Ge x O 2 on TiO 2 (001) substrates up to x = 0.54 and coherent perovskite SrSn 1- x Ge x O 3 on GdScO 3 (110) substrates up to x = 0.16. Characterization and first-principles calculations corroborate that germanium occupies the tin site, as opposed to the strontium site. These findings confirm the viability of the GTIP precursor for the growth of germanium-containing oxides by hybrid molecular beam epitaxy, thus providing a promising route to high-quality perovskite germanate films.

36 MATERIALS SCIENCE↗
DOE OSTI2023

On the potentially transformative role of auxiliary-field quantum Monte Carlo in quantum chemistry: A highly accurate method for transition metals and beyond

Approximate solutions to the ab initio electronic structure problem have been a focus of theoretical and computational chemistry research for much of the past century, with the goal of predicting relevant energy differences to within “chemical accuracy” (1 kcal/mol). For small organic molecules, or in general, for weakly correlated main group chemistry, a hierarchy of single-reference wave function methods has been rigorously established, spanning perturbation theory and the coupled cluster (CC) formalism. For these systems, CC with singles, doubles, and perturbative triples is known to achieve chemical accuracy, albeit at O(N7) computational cost. In addition, a hierarchy of density functional approximations of increasing formal sophistication, known as Jacob’s ladder, has been shown to systematically reduce average errors over large datasets representing weakly correlated chemistry. However, the accuracy of such computational models is less clear in the increasingly important frontiers of chemical space including transition metals and f-block compounds, in which strong correlation can play an important role in reactivity. A stochastic method, phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC), has been shown to be capable of producing chemically accurate predictions even for challenging molecular systems beyond the main group, with relatively low O(N3 − N4) cost and near-perfect parallel efficiency. Herein, we present our perspectives on the past, present, and future of the ph-AFQMC method. We focus on its potential in transition metal quantum chemistry to be a highly accurate, systematically improvable method that can reliably probe strongly correlated systems in biology and chemical catalysis and provide reference thermochemical values (for future development of density functionals or interatomic potentials) when experiments are either noisy or absent. Finally, we discuss the present limitations of the method and where we expect near-term development to be most fruitful.

Chemistry↗
DOE OSTI2023

Characterizing random-singlet state in two-dimensional frustrated quantum magnets and implications for the double perovskite Sr 2 CuTe 1 – x W x O 6

Motivated by the experimental observation of a nonmagnetic phase in compounds with frustration and disorder, we study the ground state of a spin-1/2 square-lattice Heisenberg model with randomly distributed nearest-neighbor J 1 and next-nearest-neighbor J 2 couplings. By using the density matrix renormalization group (DMRG) calculation on a cylinder system with a circumference of up to ten lattice sites, we identify a disordered phase between the Néel and stripe magnetic phase with growing J 2 /J 1 in the presence of strong bond randomness. The vanished spin-freezing parameter indicates the absence of spin-glass order. The large-scale DMRG results unveil the size-scaling behaviors of the spin-freezing parameter, the power-law decay of the average spin correlation, and the exponential decay of the typical spin correlation, which all agree with the corresponding behavior in the one-dimensional random-singlet (RS) state and characterize the RS nature of this disordered phase. The DMRG simulation also provides insights and opportunities for characterizing a class of nonmagnetic states in two-dimensional frustrated magnets with disorder. Here, we also compare with existing experiments and suggest more measurements for understanding the spin-liquid-like behaviors in the double perovskite Sr 2 CuTe 1–x W x O 6 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Partitioning of Complex Fluids at Mineral Surfaces

This report summarizes the results obtained during the LDRD project entitled "Partitioning of Complex Fluids at Mineral Interfaces." This research addressed fundamental aspects of such interfaces, which are relevant to energy-water applications in the subsurface, including fossil energy extraction and carbon sequestration. This project directly addresses the problem of selectivity of complex fluid components at mineral-fluid interfaces, where complex fluids are defined as a mixture of hydrophobic and hydrophilic components: e.g., water, aqueous ions, polar/nonpolar organic compounds. Specifically, this project investigates how adsorption selectivity varies with surface properties and fluid composition. Both experimental and molecular modeling techniques were used to better understand trends in surface wettability on mineral surfaces. The experimental techniques spanned the macroscale (contact angle measurements) to the nanoscale (cryogenic electronic microscopy and vibrational spectroscopy). We focused on an anionic surfactant and a well-characterized mineral phase representative of clay phases present in oil- and gas-producing shale deposits. Collectively, the results consistently demonstrate that the presence of surfactant in the aqueous fluid significantly affects the mineral-fluid interfacial structure. Experimental and molecular modeling results reveal details of the surfactant structure at the interface, and how this structure varies with surfactant coverage and fluid composition.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2022

Less Common Topological Phenomena in Bulk Materials

"Prediction and subsequent discovery of topological insulators is considered to be one of the main results in condensed matter physics in the last decades. Not surprisingly, it has received major attention of both researchers and funding agencies. This attention is well-deserved; yet, one cannot but note that nearly all this research revolves about essentially the same concept: electronic excitations with linear dispersion, covering, of course, such diverse and intriguing phenomena as topological insulator, bulk Dirac states (or Weyl, if not spin degenerate), Mayorana fermions. In this project, we will address, mainly, other topological phenomena, such as topologically nontrivial magnetic patterns (as, for instance, topological Hall and related phenomena). Specifically, we propose three interrelated trusts: (1) Time-reversal symmetry breaking nonrelativistic antiferromagnets, called altermagnets. These are materials that break Kramers degeneracy of electronic bands, despite having zero net magnetization by symmetry and being fully collinear, and not necessarily non-centrosymmetric. The corresponding band structure is very similar to the band structure in non-centrosymmetric spin-orbital materials, but materials that we propose to study are distinctly different, first and foremost in the sense that despite sharing many aspects of their electronic properties with the latter, they break the time-reversal symmetry without either spin-orbit coupling or lack of inversion symmetry. (2) Topologically nontrivial magnetic spirals. The PI has been engaged with the experimental group of Dr. Ghimire at GMU investigating Dirac materials with helical magnetism, based on stacked magnetic Kagome layers, with a generic formula of RMn6Sn6. In particular, Y Mn6Sn6 demonstrates a component of the Hall effect that is naturally interpreted in terms of a topological spin texture, as well as linear magnetoresistance. Our calculation identify Dirac states that are robust with respect to the spiral formation, and let us derive an advance mean-field model explaining the observed phase diagram. This model predicted four distinct phases, with very distinct properties, which have now been seen in neutron experiments. The same compound is known to demonstrate topological Hall effect in a particular magnetic phase, and only at elevated temperature. Based on our understanding of the phase diagram, we have worked out a phenomenological theory of a chiral (skyrmionic) response to an external magnetic field, similar to the nematic response to external strain in Fe-based superconductors, which is possible in a centrosymmetric lattice and without interplanar Dzyaloshinskii-Moriya interaction. This phenomenological theory agrees quantitatively with the experiment. It is in our plans to research other similar materials for this effect. (3) Search for 3D analogues of Fe-based superconductors. We want to investigate materials that can be viewed as 3D analogues of FeSe. Specifically, we want materials that are good metals and host antiferromagnetism, which can be suppressed by pressure and generate an s-wave superconductivity, as in Fe-based superconductors. We have in mind some candidates already. This work will proceed in close collaboration with the experimental group of Prof. Nirmal Ghimire in the same department, whose expertise lies in sample making, magnetometry and transport measurements of materials with complex magnetic structures."

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗