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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Evaluation of cosmogenic production of 39 Ar and 42 Ar for rare-event physics using underground argon

Underground argon (UAr) with lower cosmogenic activities of 39 Ar and 42 Ar has been planned as a detector in detecting scintillation light and charge collection using time projection chambers for dark matter searches and as a veto detector in suppressing backgrounds for neutrinoless double beta decay (0$vββ$ ) experiments. Long-lived radioactive isotopes, 39 Ar and 42 Ar, can also be produced on the surface when UAr is pumped out from a deep well. Understanding the production of long-lived isotopes in Ar is important for utilizing UAr for dark matter and 0$vββ$ experiments in terms of its production, transportation, and storage. Ar exposure to cosmic rays at sea-level is simulated using Geant4 for a given cosmic ray muon, neutron, and proton energy spectrum. Here we report the simulated cosmogenic production rates of 39 Ar, 42 Ar, and other long-lived isotopes at sea-level from fast neutrons, high energy muons, and high energy protons. Total production rates of 938.53/kg Ar day and 5.81 × 10 -3 /kg Ar day for 39 Ar and 42 Ar are found from our simulation. Utilizing these production rates, we set a time limit of 954 days constrained by the production of 39 Ar for UAr to be on the surface before it compromises the sensitivity for a dark matter experiment. Similarly, a time limit of 1702 days constrained by the production of 42 Ar is found for a 0$vββ$ experiment.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Dark Matter Search Results from 4.2 Tonne−Years of Exposure of the LUX-ZEPLIN (LZ) Experiment

We report results of a search for nuclear recoils induced by weakly interacting massive particle (WIMP) dark matter using the LUX-ZEPLIN (LZ) two-phase xenon time projection chamber. This analysis uses a total exposure of 4.2 ±0.1 tonne-years from 280 live days of LZ operation, of which 3.3 ± 0.1 tonne-years and 220 live days are new. A technique to actively tag background electronic recoils from 214 Pb 𝛽 decays is featured for the first time. Enhanced electron-ion recombination is observed in two-neutrino double electron capture decays of 124 Xe, representing a noteworthy new background. After removal of artificial signal-like events injected into the dataset to mitigate analyzer bias, we find no evidence for an excess over expected backgrounds. World-leading constraints are placed on spin-independent (SI) and spin-dependent WIMP-nucleon cross sections for masses ≥9 GeV/𝑐 2 . The strongest SI exclusion set is 2.2×10 −48 cm 2 at the 90% confidence level and the best SI median sensitivity achieved is 5.1 ×10 −48 cm 2 , both for a mass of 40 GeV/𝑐 2 .

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Non-symmetric pinning of topological defects in living liquid crystals

Topological defects, such as vortices and disclinations, play a crucial role in spatiotemporal organization of equilibrium and non-equilibrium systems. The defect immobilization or pinning is a formidable challenge in the context of the out-of-equilibrium system, like a living liquid crystal, a suspension of swimming bacteria in lyotropic liquid crystal. Here we control the emerged topological defects in a living liquid crystal by arrays of 3D-printed microscopic obstacles (pillars). Our studies show that while –1/2 defects may be easily immobilized by the pillars, +1/2 defects remain motile. Due to attraction between oppositely charged defects, positive defects remain in the vicinity of pinned negative defects, and the diffusivity of positive defects is significantly reduced. Experimental findings are rationalized by computational modeling of living liquid crystals. Our results provide insight into the engineering of active systems via targeted immobilization of topological defects.

42 ENGINEERING↗
DOE OSTI2020

Feedback regulation of crystal growth by buffering monomer concentration

Abstract Crystallization is a ubiquitous means of self-assembly that can organize matter over length scales orders of magnitude larger than those of the monomer units. Yet crystallization is notoriously difficult to control because it is exquisitely sensitive to monomer concentration, which changes as monomers are depleted during growth. Living cells control crystallization using chemical reaction networks that offset depletion by synthesizing or activating monomers to regulate monomer concentration, stabilizing growth conditions even as depletion rates change, and thus reliably yielding desired products. Using DNA nanotubes as a model system, here we show that coupling a generic reversible bimolecular monomer buffering reaction to a crystallization process leads to reliable growth of large, uniformly sized crystals even when crystal growth rates change over time. Buffering could be applied broadly as a simple means to regulate and sustain batch crystallization and could facilitate the self-assembly of complex, hierarchical synthetic structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Projected WIMP sensitivity of the LUX-ZEPLIN dark matter experiment

LUX-ZEPLIN (LZ) is a next generation dark matter direct detection experiment that will operate 4850 feet underground at the Sanford Underground Research Facility (SURF) in Lead, South Dakota, USA. Using a two-phase xenon detector with an active mass of 7 tonnes, LZ will search primarily for low-energy interactions with Weakly Interacting Massive Particles (WIMPs), which are hypothesized to make up the dark matter in our galactic halo. In this paper, the projected WIMP sensitivity of LZ is presented based on the latest background estimates and simulations of the detector. For a 1000 live day run using a 5.6 tonne fiducial mass, LZ is projected to exclude at 90% confidence level spin-independent WIMP-nucleon cross sections above $1.6 \times 10^{-48}$ cm$^{2}$ for a 40 $\mathrm{GeV}/c^{2}$ mass WIMP. Additionally, a $5\sigma$ discovery potential is projected reaching cross sections below the existing and projected exclusion limits of similar experiments that are currently operating. For spin-dependent WIMP-neutron(-proton) scattering, a sensitivity of $2.7 \times 10^{-43}$ cm$^{2}$ ($8.1 \times 10^{-42}$ cm$^{2}$) for a 40 $\mathrm{GeV}/c^{2}$ mass WIMP is expected. With underground installation well underway, LZ is on track for commissioning at SURF in 2020.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Accelerating Surface Radiation Content to Investigate the Impact of Radon Progeny on Superconducting Qubits

Ionizing radiation in the form of $α$, $β$, $γ$, and additional high-energy particles can induce decoherence via phonon and quasiparticle poisoning in superconducting qubits. Recent studies have explored this effect using cosmic rays or controlled radioactive sources held in the proximity of a qubit package, and have concluded that reductions in such ``external'' environmental radiation may benefit stable operation of qubit devices. However, the effect of long-lived, unstable daughters of $^{222}$Rn that ``plate out'' directly on device and packaging surfaces has not been as extensively explored. This plate-out process, well-known to the dark matter direct detection field, occurs throughout the fabrication and testing lifecycle of a device and (separately) its packaging, and produces a local source of $α$-decays which can remain active for decades. As this scales with chip area, understanding and managing this source of ionizing radiation is relevant for successfully scaling quantum computing architectures to larger numbers of qubits in a radiation-robust way. We present a setup capable of accelerating and enhancing radon daughter plateout by a factor of $7\times10^4$ over ambient, in order to study, \textit{in situ}, the impact of these events on superconducting qubits. We also provide outlook on the potential impact of this source of ionizing radiation on current and future qubit arrays.

Poudel, Sagar S. [South Dakota Sch. Mines Tech.]↗
DOE OSTI2020

Collaborative Research: Natural Organic Matter and Microbial Controls on Mobilization/Immobilization of I and Pu in Soils and Waters Affected by Radionuclide Releases in USA and Japan

In this project, the relationship between natural organic matter (NOM) and two radioactive elements that are relevant to nuclear waste disposal were studied: Plutonium (Pu) and Iodine. The human and environmental risks associated with Pu stem mainly from the very long half-lives of several of its isotopes ( 238 Pu, 88 yr; 239 Pu, 24,100 yr; 240 Pu, 6560 yr) and its radiotoxicity. Understanding Pu biogeochemical behavior in both near-field (>10-11M) and far-field scales (<10-11M) is imperative to the development of approaches for reprocessing Pu, remediation of Pu contamination and accurate assessment of risks posed by disposal practices for Pu-bearing wastes. The environmental mobility of Pu can be affected by redox potential, pH, adsorption, precipitation, complexation, colloid formation, and microbial activity, of which the first characteristic has the most profound influence. Numerous studies have shown high affinity of Pu towards NOM, as well as to mineral phases. NOM is ubiquitous in the environment, e.g., both fulvic and humic acids are able to reduce Pu(V,VI) to Pu(IV) and the redox potential of NOM is positively related to the abundance of phenolic/acidic OH groups. NOM can either facilitate or limit actinide migration, depending on specific biogeochemical conditions including pH, mineral and organic matter characteristics, etc. The other radionuclide of interest is radioiodine ( 129 I). 129I is a major by-product of nuclear fission and of serious concern to the Department of Energy (DOE) as it is among the top risk drivers at existing and potential radiowaste-contaminated sites. The risk of 129 I stems largely from its high bioconcentration factor (90% of the body’s iodine is accumulated in the thyroid), a high inventory at source terms, a very long-half life (16M years), and rapid mobility in the subsurface environment. As a consequence, 129 I has the lowest drinking water standard (1 pCi/L) among all radionuclides in the Federal Register. With a novel and sensitive gas chromatography-mass spectrometry (GC-MS) method developed in our lab, it is possible to quickly and simultaneously determine the distribution of 129 I and stable 127 I forms in environments, as low as 2 pCi/L for 129 I. This method was subsequently validated using accelerator mass spectroscopy, AMS. IO 3 - and organo-I were determined as major species in the groundwater of SRS and the Hanford Site, contrary to thermodynamic predictions that I- should be the dominant species at these sites. Mobility of 129 I was also demonstrated to depend greatly on the I species and its concentration, sediment pH, and redox state, with times to achieve equilibrium taking up to 12 weeks. Along the groundwater pathway in the F-Area of SRS, 129 I- supplied from the seepage basins was transformed to 129 IO 3 - and organo- 129 I with increasing iodine sediment sorption, causing the lower total 127 I and 129 I concentrations along the gradient transect of the waste plume. By contrast, groundwater 129 I concentrations in the wetlands (as high as 1617.3 pCi/L) were greatly elevated with respect to the source term (159.3 pCi/L). While the NOM promoted the uptake of 129 I to the wetland sediment, it also promoted the formation of soluble organic fraction. A small fraction of NOM that is bound to iodine can behave as a mobile organo-I source. Iodide was enzymatically incorporated into NOM, whereas both iodide and iodate were abiotically bound to NOM, under certain conditions. Iodate removal from the mobile aqueous phase can also occur through incorporation into carbonate (e.g., at the Hanford Site, USA). Thus immobilization and re-mobilization of iodine species were influenced by pH, Eh and the presence of NOM and metal oxides, which adds to the complexity of site remediation action. A ground-breaking result was to elucidate the products (i.e. organo-iodine moieties formed via enzymatic and non-enzymatic processes) at the molecular level by nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS). We found that iodine-NOM interactions may be influenced by NOM hydrophobic aliphatic moieties. From the perspective of ESI-FTICRMS, organo-iodine formulas were ascribed to the groups of unsaturated hydrocarbons, lignins and proteins. Iodate is likely abiotically reduced to reactive iodine species by lignin- and tannin-like compounds or carboxylic-rich alicyclic molecules (CRAM). We also investigated microbial mechanisms in iodine incorporation into NOM. We established that soil bacteria isolated from F-Area of SRS did not accumulate significant amounts of I- (0.2-2%). Intracellular uptake of I- decreases with increasing pH when pH ranged from 4 to 6. In contrast, 44 out of 84 strains isolated from the F-Area of SRS can transform I- to IO 3 - and organo-iodine. In some cases, oxidation was facilitated in the presence of H 2 O 2 . Microbes can also excrete organic acids that enhance I- oxidation by lowering the ambient pH and reacting with H 2 O 2 to form peroxy carboxylic acids. At lower pH values (≤5), H 2 O 2 hydrolysis was the driving force for iodide-oxidation; whereas, at pH ≥ 6, spontaneous decomposition of peroxy carboxylic acids, originating from H 2 O 2 and organic acids were the primary cause of iodide oxidation. Lastly, it was determined that microbial processes involved in Mn (II) are capable of directly oxidizing I- via enzymatic catalysis (i.e., multicopper oxidases), or indirectly through the formation of reactive oxygen species (ROS) and/or biogenic manganese oxides. ROS-mediated oxidation of I- was found to predominate at pH >5, whereas the enzymatic and Mn oxide pathways were more active at pH < 5. Together, this project has resulted in 9 publications in high-impact journals, and the training of 1 Ph.D and 4 undergraduate students.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Low soil phosphorus availability triggers maize growth stage specific rhizosphere processes leading to mineralization of organic P

Phosphorus (P) is one of the essential nutrients for all living organisms. High-quality mineral P fertilizer is a finite resource with only an estimated 80-100 years of reserves remaining globally. Both plants and microbes have developed several mechanisms such as secretion of organic acids, acidification of the rhizosphere, and production of extracellular enzymes to enhance the acquisition of P from soils. Increased activity of phosphatase occurs in response to P deficiency as part of P starvation responses which catalyze the hydrolysis of P o from soil organic matter (SOM) and release inorganic P (P i ). However, the specific interactions between plants and microbial communities in the rhizosphere soil triggered by P deficiency are largely unknown. In a greenhouse study we grew maize plants in low and high P containing soils and examined the role of rhizosphere processes on mineralization of organic P (P o ) in soils with low and high P availability and different P speciation 23 (Po dominated versus P i dominated) and determine its effect on plant growth. Plant biomass was determined and rhizosphere soils, and soil samples from pots with and without plants were collected at key vegetative growth stages (VGS). A variety of biogeochemical parameters (e.g. microbial biomass C and P, potential phosphatase activities, plant biomass P, soil P species etc.) were determined using both conventional (sequential chemical extraction) and advanced (e.g. high resolution mass spectrometry (FTICR-MS) and 3129 P solution NMR) techniques. Here, we used phospholipid fatty acid (PLFA) and DNA based microbial community analysis to track changes in microbial community structure and diversity. Low P availability induced changes in biogeochemical processes and microbial community composition in the rhizosphere soils of plants grown in low P containing soil. At early VGS, the plants in low P soil were visually struggling which correlated with greater rhizosphere potential acid phosphatase activity and a reduction in P o fractions. At late VGS, the plants appeared to recover which correlated with a decrease in Meh (III) extractable P, an increase in microbial biomass C and P and greater total P in the plant biomass (roots, shoots and leaves). In high P containing soil, on the other hand, greater P availability masked these rhizosphere processes. Our results confirmed the degradation of SOM and Po mineralization in rhizosphere soils driven by microbe and plant need for P. P deficiency may have favored the abundance of fungi which utilized easily degradable root exudates for the production of extracellular enzymes responsible for the mineralize of SOM P o . This study highlights the intertwined mechanisms involved, and emphasizes the importance of, P o sources for plant nutrition and survival in marginal soils.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Biotropic liquid crystal phase transformations in cellulose-producing bacterial communities

Biological functionality is often enabled by a fascinating variety of physical phenomena that emerge from orientational order of building blocks, a defining property of nematic liquid crystals that is also pervasive in nature. Out-of-equilibrium, “living” analogs of these technological materials are found in biological embodiments ranging from myelin sheath of neurons to extracellular matrices of bacterial biofilms and cuticles of beetles. However, physical underpinnings behind manifestations of orientational order in biological systems often remain unexplored. For example, while nematiclike birefringent domains of biofilms are found in many bacterial systems, the physics behind their formation is rarely known. Here, using cellulose-synthesizing Acetobacter xylinum bacteria, we reveal how biological activity leads to orientational ordering in fluid and gel analogs of these soft matter systems, both in water and on solid agar, with a topological defect found between the domains. Furthermore, the nutrient feeding direction plays a role like that of rubbing of confining surfaces in conventional liquid crystals, turning polydomain organization within the biofilms into a birefringent monocrystal-like order of both the extracellular matrix and the rod-like bacteria within it. We probe evolution of scalar orientational order parameters of cellulose nanofibers and bacteria associated with fluid-gel and isotropic-nematic transformations, showing how highly ordered active nematic fluids and gels evolve with time during biological-activity-driven, disorder-order transformation. In conclusion, with fluid and soft-gel nematics observed in a certain range of biological activity, this mesophase-exhibiting system is dubbed “biotropic,” analogously to thermotropic nematics that exhibit solely orientational order within a temperature range, promising technological and fundamental-science applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Water aging and the quality of organic carbon sources drive niche partitioning of the active bathypelagic prokaryotic microbiome

Abstract Due to the scarcity of organic matter (OM) sources in the bathypelagic (1000–4000 m depth), prokaryotic metabolism is believed to be concentrated on particles originating from the surface. However, the structure of active bathypelagic prokaryotic communities and how it changes across environmental gradients remains unexplored. Using a combination of 16S rRNA gene and transcripts sequencing, metagenomics, and substrate uptake potential measurements, here we aimed to explore how water masses aging and the quality of OM influence the structure of the active microbiome, and the potential implications for community function. We found that the relative contribution of taxa with a free‐living lifestyle to the active microbiome increased in older water masses that were enriched in recalcitrant OM, suggesting that these prokaryotes may also play a substantial role in the bathypelagic metabolism of vast areas of the ocean. In comparison to particle‐associated prokaryotes, free‐living prokaryotes exhibited lower potential metabolic rates, and harbored a limited number of two‐component sensory systems, suggesting they have less ability to sense and respond to environmental cues. In contrast, particle‐associated prokaryotes carried genes for particle colonization and carbohydrate utilization that were absent in prokaryotes with a free‐living lifestyle. Consistently, we observed that prokaryotic communities inhabiting older waters displayed reduced abilities to colonize particles, and higher capabilities to use complex carbon sources, compared to communities in waters with a higher proportion of labile OM. Our results provide evidence of regionalization of the bathypelagic active prokaryotic microbiome, unveiling a niche partitioning based on the quality of OM.

Marine & Freshwater Biology↗
DOE OSTI2022

Uranium sorption to organic matter and long-term accumulation in a pristine alpine wetland

Understanding the controls on uranium (U) mobility in the environment is key to improve the management of sites contaminated by U mining activities. Previous research has shown that natural or engineered wetlands are particularly able to scavenge high amounts of U(VI) and U(IV) under noncrystalline forms. However, questions remain on the respective roles of sorption and reduction processes in the removal of U from running waters in wetlands, as well as on the long-term stability of U storage. Here, we performed a series of geochemical, isotopic ($δ$ 238 U, ( 234 U/ 238 U)), microscopic (SEM-EDXS, EPMA) and spectroscopic (µ-XRF, µ-XAS, XANES and EXAFS at the U L 3 and M 4 -edges and Fe K-edge) investigations to determine the modes of U accumulation and assess U mobility in a natural exceptionally U-enriched (up to 5000 µg/g) wetland on the shore of Lake Nègre (Mediterranean Alps, France). Uranium (VI) was largely dominant in the two studied soil cores, except a few samples containing as much as ~50 % U(IV). At the particle scale, U is associated to a variety of organic constituents of the soil matrix with a homogenous oxidation state. Bulk EXAFS spectroscopy at the U L 3 -edge shows that U is mostly mononuclear, with dominant monodentate binding to organic moieties (C neighbors at ~3.45 Å). An additional minor fraction of U under polymeric forms is inferred from wavelet (CCWT) analysis of the EXAFS data. These observations are reinforced by 1 M bicarbonate extractions that result in the dissolution of 82–96 % of total U, including putative polymeric species. At the wetland scale, similar or slightly fractionated isotopic ratios ($δ$ 238 U) between the wetland-feeding creek waters and the wetland soils are observed, supporting the idea that U(VI) sorption on organic matter is the primary U scavenging mechanism. Furthermore, it indicates that partial U(VI) reduction to U(IV) occurs as a second step, after sorption. Analysis of U decay chain disequilibria in the cores as a function of depth suggests that U accumulation in this wetland has lasted for several thousand years. In conclusion, we propose that the wetland acts as an active reactor where U has been massively accumulating for ~14500 years, especially as U(VI) forms associated to organic matter and is further partly exported to the lake through soil erosion.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2022

Production of hydrogen peroxide in an intra-meander hyporheic zone at East River, Colorado.

The traditionally held assumption that photo-dependent processes are the predominant source of H 2 O 2 in natural waters has been recently questioned by an increasing body of evidence showing the ubiquitiousness of H 2 O 2 in dark water bodies and in groundwater. In this study, we conducted field measurement of H 2 O 2 in an intra-meander hyporheic zone and in surface water at East River, CO. On-site detection using a sensitive chemiluminescence method suggests H 2 O 2 concentrations in groundwater ranging from 6 nM (at the most reduced region) to ~ 80 nM (in a locally oxygen-rich area) along the intra-meander transect with a maxima of 186 nM detected in the surface water in an early afternoon, lagging the maximum solar irradiance by ~1.5 h. Our results suggest that the dark profile of H 2 O 2 in the hyporheic zone is closely correlated to local redox gradients, indicating that interactions between various redox sensitive elements could play an essential role. Due to its transient nature, the widespread presence of H 2 O 2 in the hyporheic zone indicates the existence of a sustained balance between H 2 O 2 production and consumption, which potentially involves a relatively rapid succession of various biogeochemically important processes (such as organic matter turnover, metal cycling and contaminant mobilization). More importantly, this study confirmed the occurrence of reactive oxygen species at a subsurface redox transition zone and further support our understanding of redox boundaries on reactive oxygen species generation and as key locations of biogeochemical activity.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2025

Arsenic Accumulation in Microbial Biomass and the Interpretation of Signals of Early Arsenic‐Based Metabolisms

Carbonaceous particles that concentrate arsenic in microbialites as old as ~3.5 Ga are similar to As-rich organic globules in modern microbialites. The former particles have been interpreted as tracers of As cycling by early microbial metabolisms. However, it is unclear if arsenic accumulation is a consequence of biological activity or passive postmortem binding of arsenic by organic matter during diagenesis in volcanically influenced, As-rich environments. Here, we address this uncertainty by evaluating the concentrations, speciation, and detectability of As in active or heat-killed biofilms formed by cyanobacteria or anoxygenic photosynthetic microbes exposed to environmentally relevant concentrations of As(III) or As(V) (50 μM to 3 mM). The genomes or metagenomes of these biofilms contain genes involved in detoxifying or energy-yielding As metabolisms. Biomass accumulates As from the solution in a concentration-dependent manner and with a preference for oxidized As(V) over As(III). Autoclaved biomass accumulates As even more strongly than active biomass, likely because living biofilms actively detoxify As. Active biofilms oxidize and reduce As and accumulate both As(III) and As(V), whereas a small fraction of As(V) can be reduced in inactive biofilms that bind As during diagenesis. Arsenic enrichments in the biomass are detectable by X-ray based spectroscopy techniques (XRF, EPMA-WDS) that are commonly used to analyze geological materials. These findings enable the reconstruction of past active and passive interactions of microbial biomass with arsenic in fossilized microbial biofilms and microbialites from the early Earth.

Madrigal‐Trejo, David↗
DOE OSTI2023

Charge Concentration Limits the Hydrogen Evolution Rate in Organic Nanoparticle Photocatalysts

Colloidal organic nanoparticles have proven to be a promising class of photocatalyst for performing the Hydrogen Evolution Reaction (HER) due to their dispersibility in aqueous environments, their strong absorption within the visible region, and the tunabilty of their component materials' redox potentials. Currently, there is little understanding of how charge generation and accumulation in organic semiconductors change when these materials are formed into nanoparticles that share a high interfacial area with water, nor is it known what mechanism limits the hydrogen evolution efficiency in recent reports on organic nanoparticle photocatalysts. Herein, we use Time-Resolved Microwave Conductivity to study aqueous-soluble organic nanoparticles and bulk thin films composed of various blend ratios of the non-fullerene acceptor EH-IDTBR and conjugated polymer PTB7-Th and examine the relationship between composition, interfacial surface area, charge carrier dynamics, and photocatalytic activity. We quantitatively measure the rate of Hydrogen Evolution Reaction by nanoparticles composed of various donor:acceptor blend ratio compositions and find that the most active blend ratio displays a Hydrogen Quantum Yield of 0.83% per photon. Moreover, we find that nanoparticle photocatalytic activity corresponds directly to charge generation, and that nanoparticles have 3x more long-lived accumulated charges relative to bulk samples of the same material composition. Here these results suggest that, under our current reaction conditions, with approximately 3x solar flux, catalytic activity by these nanoparticles is limited by the concentration of electrons and holes in operando and not a finite number of active surface cites or the catalytic rate at the interface. This provides a clear design goal for the next generation of efficient photocatalytic nanoparticles.

08 HYDROGEN↗
DOE OSTI2022

Command of active and responsive elastomers by topological defects and patterns

The project resulted in the development of stimuli-responsive elastomer coatings formed by photopolymerized liquid crystal molecules. The molecular orientation of the liquid crystal elastomers is coupled to rubber-like elasticity. The project developed an approach to produce complex patterns of molecular orientation in elastomers by employing photopatterning technique based on plasmonic metamasks that convert unpolarized incoming light into a transmitted light beam with spatially-varying linear polarization. The polarization-modulated light beam aligns the film of azodye molecules, which serves as the substrate for liquid crystal elastomer coating. The alignment of the azodye molecules follows the polarization pattern with a phase shift of the alignment direction by 90 degrees. The azodye substrate imposes orientation of molecules in the adjacent liquid crystal layer which is preserved after the monomers are polymerized into a liquid crystal elastomer. By using differently aligned substrates one could produce various patterns of molecular orientation in the elastomer, which dictate the mechanical properties of the elastomers and their response to external stimuli such as temperature, humidity, and ultraviolet irradiation. In particular, the predesigned molecular orientation produces deterministically defined topography response of the liquid crystal coatings, in which their free surface changes from flat to either locally elevated or locally compressed, depending on whether the pre-inscribed molecular orientation is predesigned with a splay or bend deformation. The research established that the mechanism of this deterministic relation between the dynamic topography and pre-inscribed molecular orientation is rooted in the change of the tensorial order parameter that characterizes the degree of orientational order, and in the contraction/expansion of polymer molecules in response to the order parameter changes. In particular, lowering the order causes contraction of polymer globules. The work demonstrated that the dynamic topography of elastomer coatings with three-dimensional pattern of orientational order includes up and down motion of the material (along the normal to the coating) and also shifts in lateral directions. We demonstrate that the deterministic relationship between the orientational patterns and variations of coatings’ profile is caused by forces that are mathematically equivalent to active forces in the system of “pullers” or “pushers” in active matter, demonstrating universality of the out-of-equilibrium behavior. The project resulted in theoretical models that predictively describe the dynamic response of coatings. The topography of liquid crystal elastomers is sensitive to stimuli such as temperature, ultraviolet irradiation, and humidity. The applicability of the patterned approach to produce dynamic coatings was expanded from nematic elastomers to their smectic counterparts. The project combined a battery of imaging techniques to unveil the dynamic properties of the coatings, ranging from the state-of-the-art dynamic holographic microscopy to fluorescent confocal polarizing microscopy and polscope microscopy. The research uncovered potential applications of dynamic elastomer coatings, such as control placement of colloidal particles, engineering of living tissues with alignment patterns of cells that follow the orientational order of elastomer coatings. The approach developed in the project can be used to design programmable dynamic coatings with functionalities that mimic biological tissues such as skin.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Out-of-equilibrium interactions and collective locomotion of colloidal spheres with squirming of nematoelastic multipoles

Many living and artificial systems show similar emergent behavior and collective motions on different scales, starting from swarms of bacteria to synthetic active particles, herds of mammals, and crowds of people. What all these systems often have in common is that new collective properties like flocking emerge from interactions between individual self-propelled or driven units. Such systems are naturally out-of-equilibrium and propel at the expense of consumed energy. Mimicking nature by making self-propelled or externally driven particles and studying their individual and collective motility may allow for deeper understanding of physical underpinnings behind collective motion of large groups of interacting objects or beings. Here, in this work, using a soft matter system of colloids immersed into a liquid crystal, we show that resulting so-called nematoelastic multipoles can be set into a bidirectional locomotion by external oscillating electric fields. Out-of-equilibrium elastic interactions between such colloidal objects lead to collective flock-like behaviors emerging from time-varying elasticity-mediated interactions between externally driven propelling particles. Repulsive elastic interactions in the equilibrium state can be turned into attractive interactions in the out-of-equilibrium state under applied external electric fields. We probe this behavior at different number densities of colloidal particles and show that particles in dense dispersions collectively select the same direction of a coherent motion due to elastic interactions between near neighbors. In our experimentally implemented design, their motion is highly ordered and without clustering or jamming often present in other colloidal transport systems, which is promising for technological and fundamental-science applications, like nano-cargo transport, out-of-equilibrium assembly, and microrobotics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Symmetry-protected electronic metastability in an optically driven cuprate ladder

Optically excited quantum materials exhibit non-equilibrium states with remarkable emergent properties, but these phenomena are usually transient, decaying on picosecond timescales and limiting practical applications. Advancing the design and control of non-equilibrium phases requires the development of targeted strategies to achieve long-lived, metastable phases. Here, in this study, we report the discovery of symmetry-protected electronic metastability in the model cuprate ladder Sr 14 Cu 24 O 41 . Using femtosecond resonant X-ray scattering and spectroscopy, we show that this metastability is driven by a transfer of holes from chain-like charge reservoirs into the ladders. This ultrafast charge redistribution arises from the optical dressing and activation of a hopping pathway that is forbidden by symmetry at equilibrium. Relaxation back to the ground state is, hence, suppressed after the pump coherence dissipates. Our findings highlight how dressing materials with electromagnetic fields can dynamically activate terms in the electronic Hamiltonian, and provide a rational design strategy for non-equilibrium phases of matter.

36 MATERIALS SCIENCE↗