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DOE OSTI2025

FY25 Report on Water NSTF Testing: Parametric and Accident Testing with Lower Tank Inlet

The Natural Convection Shutdown Heat Removal Test Facility (NSTF) at Argonne National Laboratory has continued to generate empirical validation data on the performance of water-based reactor cavity cooling system (RCCS) for seven years. This data is actively being used to support the development of passive decay heat removal systems for advanced reactors. Distinguishing this facility are 1) the large, ½ scale of the facility and 2) its governance under an NQA-1 qualified program for producing data of the highest pedigree for advanced reactor designers and regulators. In addition to the experimental activities discussed in this report, a computational modeling program continues to support the experimental program and further accuracy and understanding of the computational models. Together, the experimental and computational work create a mutually beneficial relationship integral to the overall program objective of advancing the understanding of the RCCS technology.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2026

Techno-Economic Analysis of Geologically Connected Seawater Air Conditioning (GeoSWAC) Concept for District Cooling at the University of Puerto Rico at Rio Piedras

At the University of Puerto Rico at Rio Piedras, a central chilled water plant supplies cooling to several campus buildings, contributing significantly to electricity demand during daytime peak hours, particularly in the summer months. These operational challenges are exacerbated by Puerto Rico's tropical rainforest climate and a power grid vulnerable to frequent disruptions caused by hurricanes and tropical storms. This study presents a techno-economic analysis of the existing chilled water plant serving four representative campus buildings and introduces a conceptual alternative: the Geologically connected Seawater Air Conditioning (GeoSWAC) system. GeoSWAC leverages stable low temperatures of deep ocean water (~1 km depth), hydraulically connected to an inland well, to deliver cooling without the use of vapor-compression refrigeration. Using modeled annual cooling loads and chiller performance data, capital costs, energy consumption, and levelized cost of cooling (LCOC) were evaluated for both systems. While GeoSWAC showed higher capital costs than the chiller-based scenario, operational costs were significantly lower at $26k-$53k annually, resulting in a lower LCOC between $2.3/MWh and $8.2/MWh compared to $30.2/MWh-$33.6/MWh for the chiller scenario. These results suggest that the GeoSWAC system offers a promising, low-energy, and climate-resilient alternative for large-scale cooling in tropical coastal environments, with significant potential to reduce peak electricity demand and improve long-term system reliability.

15 GEOTHERMAL ENERGY↗

DOE OSTI2026

Digital Twin User Guide for Chelan County Public Utility District

This user manual offers a comprehensive guide for developing a Digital twin (DT) of a Kaplan turbine at Chelan County Public Utility District (Chelan PUD) using neural networks. As variable renewable generation expands, hydropower units must operate with optimal efficiency and stability. For Kaplan machines, this flexibility is achieved through coordinated control of guide vane (wicket gates) opening and runner blade pitch, which amplifies the plant’s inherent nonlinear behavior and challenges traditional physics-only modeling. The efficiency of the Kaplan turbine varies with different combinations of the guide vans (wicket gate) opening and the blade angle. Each guide van opening and blade angle has a corresponding highest efficiency point, forming a cam relationship that represents the optimal combination.The discharge of a hydraulic turbine is controlled by the opening angle of the guide vans. Therefore, for each value of head, there is a certain guide van opening and blade angle that corresponds to the highest efficiency. For a given head, different combinations of the guide van opening and blade angle have different efficiencies. Therefore, coordinate cam curves are used to describe the relationship between the wicket gate opening and blade angle with different water head. To address these challenges, the manual details a data-driven modeling and learning workflow centered on structured neural networks. The approach is designed to forecast critical operational variables—discharge flow, net head, penstock (or scroll-case) pressure, and generator electrical outputs—by leveraging real-time inputs such as the generator power control setpoint, exciter field current and field voltage, together with hydromechanical commands (e.g., gate position and, when available, runner blade-pitch angle). The neural models are trained and validated on operational data from a Kaplan unit operated by Chelan PUD, demonstrating that the structured NN architecture can learn the coupled gate–blade–electrical dynamics. The result is a robust DT that improves situational awareness and supports data-informed decision-making for Chelan PUD’s Kaplan turbine operations.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2025

Drought adaptation index (DAI) based on BLUP as a selection approach for drought-resilient switchgrass germplasm

This study introduces a Drought Adaptation Index (DAI), derived from Best Linear Unbiased Prediction (BLUP), as a method to assess drought resilience in switchgrass (Panicum virgatum L.). A panel of 404 genotypes was evaluated under drought-stressed (CV) and well-watered (UC) conditions over four consecutive years (2019–2022). BLUP-estimated biomass yields were used to calculate the DAI, which enabled classification of genotypes into four adaptation groups: very well-adapted, well-adapted, adapted, and unadapted. The DAI was compared with conventional drought tolerance indices, including the Stress Susceptibility Index (SSI), Stress Tolerance Index (STI), Geometric Mean Productivity (GMP), and Yield Stability Index (YSI). Correlation analyses demonstrated strong agreement between DAI and these indices, supporting its validity and consistency. Biplot analyses using the Genotype plus Genotype-by-Environment Interaction (GGE) and Additive Main Effects and Multiplicative Interaction (AMMI) models revealed significant genotype-by-environment interactions (GEI) and identified J222.A, J463.A, and J295.A. A as high-performing genotypes, with J222.A exhibiting greater yield stability across treatments and years. Additionally, DAI isoline curves provided a graphical representation of differential genotype performance under drought and control conditions. These visualizations aided in distinguishing genotypes with stable and superior biomass yield across contrasting environments. Overall, the BLUP-based DAI is a robust and practical selection tool that improves the accuracy of identifying drought-resilient, high-yielding switchgrass genotypes. Its integration into breeding programs offers a comprehensive framework for improving biomass productivity and stress adaptation under variable climatic conditions. The application of DAI supports the development of climate-resilient cultivars and contributes to sustainable bioenergy and forage production systems.

BLUP↗

DOE OSTI2025

A radar view of ice microphysics and turbulence in Arctic cloud systems

Ice microphysical processes are inherently complex because of their sensitivity to temperature and humidity, the diversity of ice crystal habits, and their interaction with supercooled liquid water (SCL) and turbulence. Long-term surface-based radar observations have been systematically used to unravel the different processes that affect ice particle growth. In this study, we present a statistical analysis of 6.5 years of Ka-band radar observations in Arctic cloud systems, combined with thermodynamic profiles derived from radiosonde measurements. For the first time, ice particle growth and sublimation – diagnosed from vertical gradients of radar reflectivity and mean Doppler velocity – are systematically mapped across a broad range of temperature and moisture conditions. These vertical gradients correspond closely to saturation levels relative to ice and exhibit a strong temperature dependence in supersaturated regions. Notably, distinct signatures near −15 °C are indicative of dendritic growth. Turbulence, quantified via the eddy dissipation rate (EDR), is most frequently observed in regions containing SCL. The co-occurrence of SCL and elevated turbulence results in significantly enhanced ice particle growth compared to conditions in which either is present alone. This work provides new observational constraints that are critical for improving the representation of ice microphysics in atmospheric models.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2026

Techno-Economic Analysis of Geologically Connected Seawater Air Conditioning (GeoSWAC) Concept for District Cooling at the University of Puerto Rico at Rio Piedras: Preprint

15 GEOTHERMAL ENERGY↗

DOE OSTI2026

Chemical and Radiological Compatibility Testing of 3D Printed Materials

To dramatically increase the adaptability, performance, and safety of processes in support of the Defense Waste Processing Facility (DWPF), Savannah River National Lab (SRNL) plans to perform chemical and radiological compatibility testing on a wide variety of 3D printed materials of interest. The 3D printing process provides numerous strategic operational benefits such as rapid prototyping of complex designs and geometry specific to the needs of the nuclear waste disposition process, as well as on-demand rapid prototyping and iteration with materials that aren’t as accessible through traditional manufacturing methods. Reaction chemistry in simulated waste batches can be matched closely to its radioactive counterpart, but glass reactor vessels have limitations. Vessel geometry can play a big factor in mixing transport limitations, process chemistry, and degradation reaction kinetics. In addition, additive manufacturing allows for much more detailed vessel design than traditional alternatives. Waste processing techniques in DWPF also encounter extreme chemical environments including high pH, strong acids, abrasive slurries, and significant irradiation. To meet these challenges, a matrix of various polymer, ceramic, and metal additive manufacturing materials have been exposed to a suite of chemical environments of interest as well as radioactive dose (such as gamma radiation from 60 Co) to properly test their durability under these conditions. Mass change has been monitored over a period of up to a week in these conditions, as well as added characterization for surface modification through Scanning Electron Microscopy/Electron Dispersive X-ray analysis (SEM/EDX). Further chemical characterization has been monitored through Fourier-Transform InfraRed Spectroscopy (FTIR), with planned investigation via thermal and tensile strength degradation. While the direct product of this research is identification of material(s) that can withstand specific hazardous environments encountered by the mercury water wash tank in DWPF process simulation experiments, the reference base of materials will be used for many other nuclear processes in the pursuit of rapidly developed, cost-efficient, and highly specific devices for environmental remediation and much more.

Wilson, Nathan W. [Savannah River National Laborat↗

DOE OSTI2026

Investigating the Impacts of Aqueous-Phase Processing on Organic Aerosol Chemical Climatology Using ARM and ASR Observations

This project improved understanding of how atmospheric aerosol particles form and evolve, with a focus on the role of water-driven (aqueous-phase) chemical reactions in the atmosphere. These processes occur in clouds, fog, and humid air and can significantly change the composition and properties of airborne particles, known as aerosols, which influence air quality and climate. By combining field measurements, laboratory experiments, and advanced analytical techniques, the project identified key chemical signatures that allow scientists to distinguish particles formed through aqueous processes from those formed in the gas phase. Observations from multiple environments, including wildfire smoke, urban regions, and cloud-influenced areas, show that aqueous chemistry is an important pathway for particle formation and aging. The project also developed new measurement approaches using uncrewed aerial systems (UAS) to capture how aerosol composition varies with altitude, providing critical insights into how particles interact with clouds. In addition, new data analysis frameworks were created to better interpret long-term aerosol measurements and improve characterization of particle sources and transformations. These results have been integrated into a global database of aerosol measurements and used to support atmospheric modeling efforts. Overall, the project provides important tools and knowledge to improve predictions of how aerosols affect climate and air quality, particularly through their interactions with radiation and clouds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Mechanistic Tuning of Chemical Transformations for Coupling the Geo-mimicry of Acid Gas Storage with Design Strategies to Produce Clean Energy Carriers in Multi-Phase Reaction Environments (MATTER) (Final Report)

The need to diversify approaches to produce essential energy carriers such as H 2 motivate advances in thermodynamically downhill geo-inspired pathways. Currently, more than 80% of hydrogen is produced via steam methane reforming (SMR) followed by water gas shift reaction (WGSR) pathway with the co-production of CO 2 . As an alternative to introducing CO 2 separation strategies downstream such as the use of membranes, solvents, or sorbents, geo-inspired carbon mineralization is harnessed as an alternative crystallization pathway. The thermodynamically downhill carbon mineralization pathways are hypothesized to accelerate H2 conversion while separating CO 2 . The work conducted through this project discusses the mechanisms associated with coupling the water gas shift reaction (WGSR) with carbon mineralization. In addition to harnessing Ca- and Mg-bearing oxides or hydroxides that are known to be reactive for CO 2 capture, the use of earth abundant silicate minerals such as Ca- and Mg-bearing silicates, is also investigated. Key outcomes include approaches to architect Mg-silicate with well-controlled pore size distributions, probing the enhancement in H 2 yield with inherent CO 2 suppression using Ca- and Mg-bearing oxides, hydroxides, and silicates, elucidating the changes in silicate chemistry during carbon mineralization, and exploring direct integration of carbon mineralization with WGSR and the development of separate low temperature pathway for reactive CO 2 capture and mineralization are developed.

08 HYDROGEN↗

DOE OSTI2026

Solar Thermal Energy Planner (STEP 1): A New Decision Support Tool for Solar Industrial Process Heat Applications

Solar thermal technologies are a promising technology to supply low-cost thermal energy to industrial processes, but there are often significant barriers to entry to industrial owners considering these technologies for their energy demands. To overcome this barrier and convey economic value to customers, NREL and Sandia National Laboratories developed Solar Thermal Energy Planner (STEP 1), a new web-based decision support tool for solar industrial process heat systems. At SolarPACES 2024, the STEP 1 tool was still under development; progress, methodologies, and a preliminary case study was presented. With the STEP 1 tool launch in May 2025, in this work, the initial version of the full public tool will be presented with demonstrations of its capabilities using a few case studies. First, the user's process heat needs such as location, process media (e.g., steam, air), process temperature, land availability, electricity and fuel costs, among other parameters. STEP 1 features a mapping interface that allows users to draw land and roof boundaries. The process media and temperature inform technology selection criteria modules that determine the appropriate solar thermal collection technologies, as well as congruent heat transfer media (e.g., hot water, oil, salt). Once the solar thermal technology selected, its nominal thermal production for the given site is characterized using NREL's System Advisor Model (SAM). Then, a modified version of NREL's REopt optimal sizing and dispatch optimization tool determines cost-optimal sizing. Within minutes, the user receives the results of the technoeconomics analysis, including the size and performance of the cost-optimal solar-plus-storage system. The cost of the system is compared to business-as-usual (e.g., an existing, standalone natural gas boiler). Users can download key results to store for sensitivity analyses. Examples of flat plate collector, parabolic trough, and molten salt tower applications with and without PV hybridization for different industrial facility types are presented in this work. The STEP 1 tool aims to reduce barriers to the adoption of solar heating solutions stemming from a lack of familiarity and technical background with solar system design options and costs among industry stakeholders.

14 SOLAR ENERGY↗

DOE OSTI2025

Snow ALbedo eVOlution (SALVO) Campaign Snow Depth and Related Surface Properties from April - June, 2024 in Utqiagivk, AK

Detailed transects of snow depths and related measurements were made with a magnaprobe along fixed lines in Utqiagvik, AK. The operator measures snow depth by plunging a rod with a sliding basket into the snow and pressing a trigger. At this point, the data logger records the distance between the tip of the rod and the height of the basket, the measurement number, the time, and the geographic location of the measurement. To measure snow depth, the rod tip must be placed at the snow-ground or snow-sea ice interface. The interface can be hard or soft; in the latter case, it is possible to “over-probe”, producing a snow depth that is too high. At times, the probe was also used to measure the depths of other interfaces within the snowpack (for example, the depth to persistent ice lenses) or the water depths of ponds atop the tundra or sea ice. When these alternative depth measurements were made, the operator recorded the location, measurement number, and composition of the alternative depth measurement in a field notebook. The data logger on the probe stores several thousand points. Data is downloaded to a computer at the end of a day or several days. Probes: We used 2 magnaprobes identified as GEO1 and GEODEL with the following serial numbers: S/N 20240416 (GEO1) and S/N P48066 (GEODEL). Note : There are three data levels available with this dataset: b3, b4, and a6. New users of these data are strongly encouraged to use the level a6 or b4 data.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Rising Water Levels and Vegetation Shifts Drive Substantial Reductions in Methane Emissions and Carbon Dioxide Uptake in a Great Lakes Coastal Freshwater Wetland

ABSTRACT Coastal freshwater wetlands are critical ecosystems for both local and global carbon cycles, sequestering substantial carbon while also emitting methane (CH 4 ) due to anoxic conditions. Estuarine freshwater wetlands face unique challenges from fluctuating water levels, which influence water quality, vegetation, and carbon cycling. However, the response of CH 4 fluxes and their drivers to altered hydrology and vegetation remains unclear, hindering mechanistic modeling. To address these knowledge gaps, we studied an estuarine freshwater wetland in the Great Lakes region, where rising water levels led to a vegetation shift from emergent Typha dominance in 2015–2016 to floating‐leaved species in 2020–2022. Using eddy covariance flux measurements during the peak growing season (June–September) of both periods, we observed a 60% decrease in CH 4 emissions, from 81 ± 4 g C m −2 in 2015–2016 to 31 ± 3 g C m −2 in 2020–2022. This decline was driven by two main factors: (1) higher water levels, which suppressed ebullitive fluxes via increased hydrostatic pressure and extended CH 4 residence time, enhancing oxidation potential in the water column; and (2) reduced CH 4 conductance through plants. Net carbon dioxide (CO 2 ) uptake decreased by 90%, from −267 ± 26 g C m −2 in 2015–2016 to −27 ± 49 g C m −2 in 2020–2022. Additionally, diel CH 4 flux patterns shifted, with a distinct morning peak observed in 2015–2016 but absent in 2020–2022, suggesting changes in plant‐mediated transport and a potential decoupling from photosynthesis. The dominant factors influencing CH 4 fluxes shifted from water temperature and gross primary productivity in 2015–2016 to atmospheric pressure in 2020–2022, suggesting an increased role of ebullition as a primary transport pathway. Our results demonstrate that changes in water levels and vegetation can substantially alter CH 4 and CO 2 fluxes in coastal freshwater wetlands, underscoring the critical role of hydrological shifts in driving carbon dynamics in these ecosystems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

X-ray absorption spectroscopy of lanmodulin-derived peptides bound to rare earth elements

A sustainable and robust supply chain of rare earth elements (REEs) is necessary to meet our consumer, national security and clean energy goals. However, current intra-REE separation technologies (e.g. solvent extraction) are costly and carry a heavy environmental burden. Therefore, the development of new aqueous based ligands that are selective for individual REEs will be integral in future REE production systems. To develop these ligands, an understanding of how ligand coordination structure relates to selectivity is imperative. We used X-ray absorption spectroscopy (XAS) to observe the local structure around four lanthanide (Ln) ions (La, Ce, Pr and Nd) complexed by water and several relevant chelating ligands [lanmodulin EF-hand 1 peptides (LanM1), ethylenediaminetetraacetic acid (EDTA), aminotris(methylenephosphonic acid) (ATMP) and citric acid]. To collect these liquid-phase XAS spectra, we developed a new flow cell that prevents bubble interference and beam damage to the samples. In the X-ray absorption near-edge structure (XANES), we observed energy shifts in the white line, white line broadening and differences in the white line intensity of different Ln–ligand complexes between ligands. In the extended X-ray absorption fine structure (EXAFS), we distinguished differences in peak intensity and distance between coordinating ligands. Differences in the local coordination structure between Ln–LanM1 peptide complexes were more subtle compared with the other ligands (La–water, La–EDTA, La–ATMP and La–citric acid complexes). Further XANES and EXAFS studies, in combination with modelling and other techniques, could greatly improve our structural knowledge of how these aqueous ligands bind Ln ions and how they can be used to design more selective ligands for more efficient and sustainable REE separations.

EDTA↗

DOE OSTI2025

The Impact of Naphthenic Acids on Dynamic Fluid–Fluid Interactions: Implication for Enhanced Oil Recovery

Previous coreflooding results and wettability analyses in our group show that injection of naphthenic-acid-enriched water can improve oil recovery over traditional waterflooding. This observation is still a subject of research efforts without a definitive explanation. Naphthenic acids (NA) have been reported to drive wettability alteration and increase the water–oil interface elasticity. These alterations depend on the NA carbon number and aqueous-phase salinity, among other conditions, as reported in the literature. Smart-water flooding (SWF) research often links recovery to the initial wettability condition, being higher for initially oil-wet rock. SWF refers to a technique in which the aqueous-phase ion composition or/and salinity are changed to maximize oil recovery. Given NAs’ complex solution behavior, selecting acid combinations that prompt oil recovery is a difficult objective. The aim of this research is to determine the effects of select naphthenic acids on the oil–water interfacial rheology and wettability alteration and how these interfacial effects are associated with oil recovery under spontaneous imbibition. NAs were selected based on their carbon number, molecular structure, and solubility in the saline solution used in this research. We aimed at exploring which NAs should be used to regulate interfacial properties so as to either increase oil recovery or accelerate production. Time-domain nuclear magnetic resonance, interfacial dilatational rheology, and liquid-bridge experiments, i.e., proxy of snap-off, were conducted. A baseline was established using results obtained with a previously tested sulfate-rich aqueous phase, shown to be effective in recovering oil. Results show that NA14 and N18 increase the water–oil interfacial viscoelasticity and induce interfacial healing but led to different recovery factors. N10, while effective at inducing water wetness in oil-wet rock, is ineffective at increasing the recovery factor. We concluded that wettability and oil–water interfacial rheology are not exclusive, and instead they can synergistically favor EOR benefits. Moreover, oil recovery benefits under spontaneous imbibition are shown to depend strongly on the initial wettability conditions.

Medina-Rodriguez, Bryan X. (ORCID:0000000262922831↗

DOE OSTI2025

Thermal Optimization and Experimental Demonstration of a Silicon Carbide, Half-Bridge Power Module

This paper describes modeling and experimental work to design and demonstrate a silicon carbide (SiC), single-side-cooled power module. Two SiC metal-oxide-semiconductor field-effect transistors (MOSFET) were used for each switch position and packaged on a metalized ceramic substrate. Thermal modeling was first conducted to optimize the module packaging to minimize junction-to-fluid thermal resistance and device temperature variations. This procedure identified the optimal device placement and baseplate thickness to maximize thermal performance. A heat exchanger - incorporating impinging jets of water-ethylene glycol - was designed to cool the module's baseplate to minimize thermal resistance and pumping power. The heat exchanger used relatively low fluid velocities (<1.5 m/s) to minimize erosion-corrosion effects and relatively large fluid channel sizes (>=1 mm) to prevent clogging. The power module concept was fabricated, and experiments were conducted to measure its thermal performance. Direct current was used to power the module devices, and junction temperatures were measured via device temperature-sensitive parameters. The experimental results were found to be in good agreement with model predictions (within 2%) and yielded junction-to-fluid thermal resistance values as low as about 15 mm2 K/W at relatively low pumping power values. The results demonstrate the improved performance associated with jet impingement cooling and represent an improvement over existing channel-flow-type cold plates, which can enable improvements to power density and reliability.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Hydrothermal solubility of Dy hydroxide as a function of pH and stability of Dy hydroxyl aqueous complexes from 25 to 250 °C

The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize the thermodynamic properties of Dy 3+ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ f G° T ) derived for Dy 3+ and DyOH 2+ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO 4 solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K s0 ) and formation constants for the hydrolysis of Dy (β n with n = 1 to 3; Dy 3+ + nOH – = DyOH n 3-n ) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy 3+ aqua ions and the DyOH 2+ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.

58 GEOSCIENCES↗

DOE OSTI2026

Microcanonical Kinetics of Water-Mediated Proton Transfer in 4ABAH + ·(H 2 O) n = 4–6 Clusters (ABA = Aminobenzoic Acid): A Model System for Size-Dependent Relaxation to Ergodic Behavior

Here, we leverage the unique properties of the 4ABAH + · (H 2 O) n clusters (ABA = 4-aminobenzoic acid, n = 4−6) to quantitatively address how a finite, isolated system evolves into an ergodic condition starting from localized arrangements in configuration space. This system adopts two distinct structural isomers in which water molecules cluster around the cationic centers of its two protomers with widely separated positive charge centers. These isomers arise from excess proton attachment to either the acid (O) or amino (N) group on opposite sides of the benzene ring. Both forms are captured and kinetically trapped using cryogenic ion methods and then selectively vibrationally excited through their mutually exclusive IR bands involving NH and OH stretching fundamentals. Because the IR excitation lies below the water binding energy, the system can evolve to explore slow, rare events that lead to the interconversion between the two isomers. The rates of these intracluster reactions are determined by using a pump−probe scheme involving ∼5 ns IR pump and UV probe lasers. The rates occur on the microsecond time scale, leading to steady state populations of the isomers, thus revealing the cluster size-dependent fractionation between the two species at microcanonical equilibrium. The steady state distributions are correlated with the expected trend in the cluster size-dependent reaction energetics, which are in turn consistent with changes in the relative densities of states of the two species. These results thus provide an unusually clear example in which complex, protic-solvent-mediated chemical transformations are captured within a finite system at a precisely determined internal energy.

Rana, Abhijit [Yale Univ., New Haven, CT (United S↗

DOE OSTI2025

Extracted Water Induces Concentration Fluctuations in Model Ternary Liquid–Liquid Extraction System

Organic phase aggregation and phase splitting are two important (and connected) phenomena in liquid–liquid extraction of metal ions. Previously, we demonstrated how structure in binary mixtures of extractant and diluent originates from concentration fluctuations associated with the so-called “third-phase formation” liquid–liquid phase instability. For more complex systems, we sought to understand how extracted aqueous components affect these concentration fluctuations. Here, in this study, we use small-angle X-ray scattering and molecular dynamics simulations to investigate organic phase structural changes upon contact with water in a model ternary system of water/alkane/extractant. Critical exponents were determined from scattering with temperature variation and were consistent with mean field values. Then, by controlling the water content in the organic phase through direct dissolution of fixed quantities at constant temperature, we relate the observed increase in the fluctuation length scale to changes to the spinodal temperature of the third-phase formation phase boundary. We find a roughly linear relationship between water concentration and the spinodal temperature and a similar slope in that relationship for different linear alkane diluents. This suggests that the mechanism by which water extraction impacts the organic phase structure is to enhance concentration fluctuations through the introduction of additional polar extractant-water complexes, which increases the spinodal temperature and thereby decreases the reduced temperature, i.e., the distance to the instability. This explanation for how solutes induce aggregation in liquid–liquid extraction organic phases may extend to more complex systems, explaining the large increases in correlation lengths reported under high acid and metal loading.

Bonnett, Brittany L. [Argonne National Laboratory ↗