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DOE OSTI2025

Optoelectronic polymer memristors with dynamic control for power-efficient in-sensor edge computing

Abstract As the demand for edge platforms in artificial intelligence increases, including mobile devices and security applications, the surge in data influx into edge devices often triggers interference and suboptimal decision-making. There is a pressing need for solutions emphasizing low power consumption and cost-effectiveness. In-sensor computing systems employing memristors face challenges in optimizing energy efficiency and streamlining manufacturing due to the necessity for multiple physical processing components. Here, we introduce low-power organic optoelectronic memristors with synergistic optical and mV-level electrical tunable operation for a dynamic “control-on-demand” architecture. Integrating signal sensing, featuring, and processing within the same memristors enables the realization of each in-sensor analogue reservoir computing module, and minimizes circuit integration complexity. The system achieves 97.15% fingerprint recognition accuracy while maintaining a minimal reservoir size and ultra-low energy consumption. Furthermore, we leverage wafer-scale solution techniques and flexible substrates for optimal memristor fabrication. By centralizing core functionalities on the same in-sensor platform, we propose a resilient and adaptable framework for energy-efficient and economical edge computing.

Optics↗

DOE OSTI2016

OpenACC directive-based GPU acceleration of an implicit reconstructed discontinuous Galerkin method for compressible flows on 3D unstructured grids

In this study, we use a combination of modeling techniques to describe the relationship between fracture radius that might be accomplished in a hypothetical enhanced geothermal system (EGS) and drilling distance required to create and access those fractures. We use a combination of commonly applied analytical solutions for heat transport in parallel fractures and 3D finite-element method models of more realistic heat extraction geometries. For a conceptual model involving multiple parallel fractures developed perpendicular to an inclined or horizontal borehole, calculations demonstrate that EGS will likely require very large fractures, of greater than 300 m radius, to keep interfracture drilling distances to ~10 km or less. As drilling distances are generally inversely proportional to the square of fracture radius, drilling costs quickly escalate as the fracture radius decreases. It is important to know, however, whether fracture spacing will be dictated by thermal or mechanical considerations, as the relationship between drilling distance and number of fractures is quite different in each case. Information about the likelihood of hydraulically creating very large fractures comes primarily from petroleum recovery industry data describing hydraulic fractures in shale. Those data suggest that fractures with radii on the order of several hundred meters may, indeed, be possible. The results of this study demonstrate that relatively simple calculations can be used to estimate primary design constraints on a system, particularly regarding the relationship between generated fracture radius and the total length of drilling needed in the fracture creation zone. Comparison of the numerical simulations of more realistic geometries than addressed in the analytical solutions suggest that simple proportionalities can readily be derived to relate a particular flow field.

15 GEOTHERMAL ENERGY↗

DOE OSTI2019

Effect of alloying elements on the $γ$’ antiphase boundary energy in Ni-base superalloys

Mechanical and fatigue performance of γ-γ' Ni-base superalloys are strongly affected by the antiphase boundary energy (APBE) of the γ' precipitates which, in turn, is dictated by the alloy's composition. Due to the multicomponent character of these alloys, establishing composition-APBE relationships are challenging, even though the qualitative effect of individual solutes on the APBE may be known. This work attempts to utilize density functional theory-based cluster expansion calculations to systematically assess the effect of composition on the APBE of the γ' phases in Ni-base superalloys. We aim to elucidate the influence of not only one single element but also multiple coexisting alloying elements on the γ' APBE. By explicit consideration of configurational disorder via Monte Carlo sampling, the effect of temperature on the APBE has also been analyzed. Overall, this work reveals that (1) effects of individual solute element M on the APBE energy obtained in an isolated, ternary condition (i.e. in Ni 3-x Al 1-y M x+y ) does not directly translate to a multi-solute case and that (2) the mutual synergistic interactions among different solute elements are not negligible. Based on the present results, an empirical master equation that predicts the APBE based on the composition of the γ' phases has been obtained.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Prediction and Computation of Corrosion Rates of A36 Mild Steel in Oilfield Seawater

The parameters which primarily control the corrosion rate and life of steel structures are several and they vary across the different ocean and seawater as well as along the depth. While the effect of single parameter on corrosion behavior is known, the conjoint effects of multiple parameters and the interrelationship among the variables are complex. Millions sets of experiments are required to understand the mechanism of corrosion failure. Statistical modeling such as ANN is one solution that can reduce the number of experimentation. ANN model was developed using 170 sets of experimental data of A35 mild steel in simulated seawater, varying the corrosion influencing parameters SO{sub 4}{sup 2−}, Cl{sup −}, HCO{sub 3}{sup −},CO{sub 3}{sup 2−}, CO{sub 2}, O{sub 2}, pH and temperature as input and the corrosion current as output. About 60% of experimental data were used to train the model, 20% for testing and 20% for validation. The model was developed by programming in Matlab. 80% of the validated data could predict the corrosion rate correctly. Corrosion rates predicted by the ANN model are displayed in 3D graphics which show many interesting phenomenon of the conjoint effects of multiple variables that might throw new ideas of mitigation of corrosion by simply modifying the chemistry of the constituents. The model could predict the corrosion rates of some real systems.

36 MATERIALS SCIENCE↗

DOE OSTI2018

WIPP Space Faces TRU Waste Disposal Limits; The Volume Reducing Solution - 18365

Transuranic (TRU) waste packaging for removal from a glovebox has for many years involved the use of bags as the primary containment. In many cases, many hydrogenous layers of bags, yards of tape, and multiple filters are added to the waste stream in order to get the TRU waste into the final 55 gallon drum package to be shipped and buried at the Waste Isolation Pilot Plant (WIPP). The WIPP is currently limited to a total finite disposed volume of Contact Handled (CH) and Remote Handled (RH) TRU waste. As of early 2014 over half of the allotted WIPP volume had been filled with mainly CH-TRU waste. Based on current bag operation packaging methods used, the Department of Energy's (DOE) remaining CH and RH waste will not fit in the remaining limited WIPP space. Bag operations, can be performed safely by good operators following tedious repetitive processes and many Administrative Safety Controls. Since the bag is the only confinement layer between the contamination and the operator, contamination incidents can occur. Bag-out operations require close proximity to the waste to perform the process. With some waste streams, this close to waste proximity increases operator radiation dose. Central Research Laboratories (CRL), based in Red Wing Minnesota, who for many decades has developed proven engineered material transfer solutions based around their Rapid Transfer Port (RTP) technology, has worked with DOE sites to develop a TRU Waste Management Solution. The solution is a single filtered large Polyethylene (PE) or Stainless Steel (SST) Rapid Transfer Port container in a standard Department of Transportation (DOT) 7A, Type A drum, which allows for loading of TRU waste directly from the operational glovebox without the use of bags, sleeves or tapes to provide leak tight containment. All operator interventions to connect and disconnect a drum to and from the glovebox are achieved in an upright ergonomic position by one (1) operator in less than three (3) minutes. Minimal As Low As Reasonably Achievable (ALARA) levels are achieved during connect and disconnect of the drum, due to the engineered safety controls of the RTP. The CRL RTP solution allows glovebox or re-packaged TRU waste to be safely transferred to the final 55 Gallon drum container without additional bags or tape. The high diffusion coefficient filter on the CRL RTP 55G container and elimination of added hydrogenous packaging, improves the Decay Heat Limit (DHL) per drum for most TRU waste types compared with bagged drums, and in most cases allows more TRU waste to be loaded per drum. Inorganic TRU waste materials can be packaged directly into the CRL RTP SST drum container to the maximum DHL and Fissile Gram Equivalent (FGE) allowable for a drum. This paper will show how highly efficient TRAMPAC approved TRU waste packaging of CH and RH TRU waste can be accomplished in a safer, cost effective manner without adding any additional packaging materials to the waste stream, thus increasing the chance of placing all DOE's legacy and to be generated TRU waste in the remaining WIPP space. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2014

Multiple scattering of surface waves by cavities in a half-space

Scattering of surface waves from multiple two-dimensional cavities at the surface of a homogenous, isotropic, linearly elastic half-space is analyzed in this work. For the case of multiple cavities, the scattered field is shown to be equivalent to the total radiation from the distributions of tractions, calculated from the incident wave, over the surfaces of the cavities. The multiple-scattering model is obtained from known single-scattering calculation for a cavity by the use of the self-consistent method. The second order approximation to the multiple-scattering problem by a random distribution of cavities is then considered and solved analytically. The vertical displacement at some distance from the cavities is calculated and verified by the solution of the same problem obtained by the boundary element method (BEM). The analytical and BEM results are graphically displayed and show good agreement when the depths of the cavities are small compared to the wavelength.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2018

High Density Chip Interconnect Technology Using High Density Glass Interposers

Demands for high density and high speed interconnect solutions are not satisfied by current technology offerings. Platforms such as printed circuit boards (PCBs), ceramic substrates and silicon interposers don’t provide the small form factor nor the I/O density to support 5G or 1Tbps gigabit ethernet solutions. Current solutions also don’t support die to die assembly with integrated tiled solutions for wide area and fanout solutions for lager data and signal processing. A solution with through vias provides an order of magnitude or smaller density supporting much higher density attach and assembly By fabricating a very fine pitch metal filled through glass via solution it’s possible to deliver the necessary improvements in performance, reliability, even higher data speed rates with smaller area and much denser geometries. There are a number of opportunities across a wide variety of industries for through glass interposers as they become the replacement for printed circuit boards (PCBs) and ceramic substrates. The broad array of opportunities include renewable energy, medical electronics (ME), defense electronics (DE)/space and consumer electronics (CE), but likely will impact every industry and market segment. Compared to PCBs, through glass via (TGV) solutions provide the next generation platform for semiconductor assembly improvements. The ability to generate lines, spaces, trenches and vias similar to wafer level geometries delivers wired solutions one to two orders of magnitude smaller than traditional organic PCB and ceramic substrate offerings. Higher density connections also include the thru vias that connect multiple metal layers, fanout. It’s possible to deliver filled metal vias that are 20um diameter with much tighter pitch than can be offered with PCB. Our goal is to provide 20um diameter and smaller via, 50um and smaller pitch, and aspect ratios at 25:1 and greater with hermetically metal filled vias. The goal of CVI is to replace or eliminate PCBs, ceramic substrate and through silicon vias (TSV) providing a glass interposer with metal filled, fiber plugged and/or optional wireless interconnectivity. The end plan is to deliver a glass substrate platform that provides improved electrical performance, versatility, inertness, and much improved cost and cycle time (development, drawing, and delivery) to performance in the form of small millimeter sized substrates or full 8” wafer substrates. Glass delivers an improvement over silicon thru vias (TSV) in the number of processing steps, cost, reliability and cycle time. In addition to metal plugged vias, our glass interposers are capable of fiber and antennae solutions providing two additional very high density and ultra-high speed data transfer capabilities.

36 MATERIALS SCIENCE↗

DOE OSTI2014

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

A fiber-based adsorbent and a related method of manufacture are provided. The fiber-based adsorbent includes polymer fibers with grafted side chains and an increased surface area per unit weight over known fibers to increase the adsorption of dissolved metals, for example uranium, from aqueous solutions. The polymer fibers include a circular morphology in some embodiments, having a mean diameter of less than 15 microns, optionally less than about 1 micron. In other embodiments, the polymer fibers include a non-circular morphology, optionally defining multiple gear-shaped, winged-shaped or lobe-shaped projections along the length of the polymer fibers. A method for forming the fiber-based adsorbents includes irradiating high surface area polymer fibers, grafting with polymerizable reactive monomers, reacting the grafted fibers with hydroxylamine, and conditioning with an alkaline solution. High surface area fiber-based adsorbents formed according to the present method demonstrated a significantly improved uranium adsorption capacity per unit weight over existing adsorbents.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Fiber-based adsorbents having high adsorption capacities for recovering dissolved metals and methods thereof

36 MATERIALS SCIENCE↗

NASA NTRS2017

In-Space Assembly Capability Assessment for Potential Human Exploration and Science Applications

Human missions to Mars present several major challenges that must be overcome, including delivering multiple large mass and volume elements, keeping the crew safe and productive, meeting cost constraints, and ensuring a sustainable campaign. Traditional methods for executing human Mars missions minimize or eliminate in-space assembly, which provides a narrow range of options for addressing these challenges and limits the types of missions that can be performed. This paper discusses recent work to evaluate how the inclusion of in-space assembly in space mission architectural concepts could provide novel solutions to address these challenges by increasing operational flexibility, robustness, risk reduction, crew health and safety, and sustainability. A hierarchical framework is presented to characterize assembly strategies, assembly tasks, and the required capabilities to assemble mission systems in space. The framework is used to identify general mission system design considerations and assembly system characteristics by assembly strategy. These general approaches are then applied to identify potential in-space assembly applications to address each challenge. Through this process, several focus areas were identified where applications of in-space assembly could affect multiple challenges. Each focus area was developed to identify functions, potential assembly solutions and operations, key architectural trades, and potential considerations and implications of implementation. This paper helps to identify key areas to investigate were potentially significant gains in addressing the challenges with human missions to Mars may be realized, and creates a foundation on which to further develop and analyze in-space assembly concepts and assembly-based architectures.

Jefferies, Sharon A.↗

NASA NTRS2012

Simplex GPS and InSAR Inversion Software

Changes in the shape of the Earth's surface can be routinely measured with precisions better than centimeters. Processes below the surface often drive these changes and as a result, investigators require models with inversion methods to characterize the sources. Simplex inverts any combination of GPS (global positioning system), UAVSAR (uninhabited aerial vehicle synthetic aperture radar), and InSAR (interferometric synthetic aperture radar) data simultaneously for elastic response from fault and fluid motions. It can be used to solve for multiple faults and parameters, all of which can be specified or allowed to vary. The software can be used to study long-term tectonic motions and the faults responsible for those motions, or can be used to invert for co-seismic slip from earthquakes. Solutions involving estimation of fault motion and changes in fluid reservoirs such as magma or water are possible. Any arbitrary number of faults or parameters can be considered. Simplex specifically solves for any of location, geometry, fault slip, and expansion/contraction of a single or multiple faults. It inverts GPS and InSAR data for elastic dislocations in a half-space. Slip parameters include strike slip, dip slip, and tensile dislocations. It includes a map interface for both setting up the models and viewing the results. Results, including faults, and observed, computed, and residual displacements, are output in text format, a map interface, and can be exported to KML. The software interfaces with the QuakeTables database allowing a user to select existing fault parameters or data. Simplex can be accessed through the QuakeSim portal graphical user interface or run from a UNIX command line.

Donnellan, Andrea↗

NASA NTRS2019

Supporting Crew Autonomy in Deep Space Exploration: Preliminary Onboard Capability Requirements and Proposed Research Questions. Technical Report of the Autonomous Crew Operations Technical Interchange Meeting

Communication delays are a critical challenge posed by long duration deep space exploration. Space missions historically have relied on an ever-present Mission Control Center (MCC) to direct operations in near real-time. As unanticipated anomalies that defeat fault detection and resolution systems do arise, the lack of real-time communication will significantly weaken what the MCC support represents: a reliable safety net for the flight crew through its deep and diverse areas of expertise and investigative resources. As a consequence, future space vehicles and habitats need to be equipped with capabilities to support the flight crew to operate with little or no ground support. Considerations must be given to vehicle and mission designs that will fortify the traditionally ground-centered safety net and forge new support systems, when communication delays exist. In August 2018, NASA’s Human Research Program, through its Human Factors and Behavioral Performance Element, convened a Technical Interchange Meeting (TIM) on Autonomous Crew Operations at NASA Ames Research Center. The goal of the meeting was to gather input from NASA centers, industry, academia, and branches of the Department of Defense (DoD) to address how intelligent technologies can be applied to augment onboard capabilities to support crew anomaly response. The TIM featured 24 presentations by 29 speakers and hosted a total of 59 attendees, including 43 from 5 NASA centers (Ames, Johnson, Langley, Marshall, and Jet Propulsion Lab) and 4 from the DoD (3 from Army Research Lab and 1 from Naval Postgraduate School), with remaining attendees from academia (e.g., UC Davis, CMU) and industry (e.g., IBM, Siemens). Discussions were centered around three themes: standards and guidelines, lessons learned in analog environments, and technologies. To help provide a framework for discussion, a concept matrix describing anomaly response processes was created prior to the TIM (Figure 1, page 6). The matrix captures the steps involved (monitoring and detection, diagnosis, solution development and evaluation, solution implementation and verification, resolution documentation) as well as the resources and capabilities required to support these steps (data, knowledge, analysis, synthesis, resource management). A wallpaper size printout of the matrix was utilized at the TIM to solicit attendee inputs along the three themes; the activity garnered 108 submissions of ideas. Overall, what emerged from TIM discussions was a picture of mismatch between crew anomaly response needs and support that can be provided by existing intelligent technologies. The needs are broad, spanning multiple steps and processes/resources, with many of which lacking support from existing technologies, such as knowledge management throughout the steps of problem solving (especially in resolution documentation) and manpower management. The solutions provided by existing intelligent technologies are specific to the steps/processes that they are designed to support and constrained to solving only problems similar to those that have occurred before. What is lacking from technologies is typically made up by humans, specifically their complex critical thinking, creative problem solving, and domain expertise. In the end, the TIM highlighted the pressing need to support responses to onboard anomalies during autonomous crew operations, particularly those that have eluded the system tests, inspection, and other assurance processes. Such anomalies can potentially threaten crew and vehicle safety, as well as significantly impact overall operations with additional workload. These fairly rare events are difficult to anticipate and prepare for, given the state-of-the-art in intelligent technologies. This is true even for anomalies that stem from “unknown knowns”—cases in which there is sufficient external information to characterize the problem but the overall pattern fails to be recognized by the problem solver, or in which the internal knowledge needed to solve a problem is held tacitly and potentially accessible by the problem solver but not articulated. It follows that the ability to tackle anomalies lies not only with the availability of relevant information and knowledge but also their accessibility in times of need. To that end, we propose research questions along the following three broad themes: • How intelligent technologies can help make relevant knowledge and information available? • How intelligent technologies can help make relevant knowledge and information accessible? • How intelligent technologies can help support the crew operating as a team in anomaly response processes?

autonomous crew operations↗

DOE OSTI2021

Physics-Informed Neural Network Method for Forward and Backward Advection-Dispersion Equations

Advection-dispersion equations (ADEs) are commonly used to describe transport phenomena in porous media. Even though mature discretization-based numerical methods for ADEs exist, some challenges still remain, especially when it comes to solving advection-dominated forward ADEs and diffusion-dominated backward ADEs. The latter problem usually arises in the source identification context and leads to numerically unstable grid-based solutions that require a form of regularization or should be treated as an inverse problem that is computationally more expensive because it requires solving the forward problem multiple times. In this study, we propose a discretization-free approach based on the physics-informed neural network (PINN) method for solving coupled ADE and Darcy flow equations with space-dependent hydraulic conductivity. In this approach, the hydraulic conductivity, hydraulic head, and concentration fields are approximated with deep neural networks (DNNs). We assume that the conductivity field is given by its values on a grid, and we use these values to train the conductivity DNN. The head and concentration DNNs are trained by minimizing the residuals of the flow equation and ADE and using the initial and boundary conditions as additional constraints. The PINN method is applied to one- and two-dimensional forward ADE problems, where its performance for various P\'{e}clet numbers ($Pe$) is compared with the analytical and numerical solutions. We find that the PINN method is accurate with errors of less than 1\% and outperforms some conventional discretization-based methods for $Pe$ larger that 100. Next, we demonstrate that the PINN method remains accurate for the backward ADEs, with the relative errors in most cases staying under 5\% compared to the reference concentration field. Finally, we show that when available, the concentration measurements can be easily incorporated in the PINN method and significantly improve (by more than 50\% in the considered cases) the accuracy of the PINN solution of the backward ADE.

He, Qizhi↗

DOE OSTI2020

Fluidization of Group A Glass Particles: Experiments and Preliminary Validation

This work is aimed at providing reliable high-quality data from fluidization experiments. Geldart Group A glass beads are used as bed material. The fluidizing medium is air at atmospheric pressure which enters the system at 40% relative humidity. The air inlet velocity is varied over a broad range from 2 U mf to 26 U mf , where the minimum fluidization velocity, U mf , is 0.608 cm/s. There is not a significant change in the mean values of differential pressure; however, there are noticeable trends in their standard deviation values. Preliminary validation studies are performed using the open-source software Multiphase Flow with Interphase eXchanges (MFiX) developed by the National Energy Technology Laboratory (NETL). The results from Eulerian-Eulerian (MFiX-TFM, two-fluid model) and Eulerian-Lagrangian (MFiX-PIC, particle-in-cell) formulations are compared. The work presented in this report highlights the applicability of MFiX-PIC for large-scale applications, and reveals that PIC simulation offers a suitable alternative to TFM simulation when effects due to multiple components or polydispersity are significant. PIC modeling provides a readily extendible framework for such systems. However, PIC models do rely on an empirical closure for inter-particle stress. Some solution discrepancies were evident in MFiX-PIC predictions which require further analysis. As such, the study underlines the need for a systematic approach to quantify the sources of numerical uncertainty within the PIC model. However, even with known empiricism, MFiX-PIC has demonstrated considerable potential in analyzing gas-solid systems. The results obtained are encouraging and warrant further investigation to improve the predictive capability of MFiX-PIC.

36 MATERIALS SCIENCE↗

NASA NTRS1973

Gravitational perturbations of equatorial orbits.

Asymptotic solutions are developed for the motion of a geocentric satellite in the equatorial plane due to gravitational perturbations such as nonsphericity (especially oblateness) of the primary body. Axisymmetric potentials are considered. A class of transformations is developed and the equations of motion are solved by the method of generalized multiple scales. Further it is shown that the equations of motion can be transformed into the required form to within any specified degree of accuracy. The transformations form an Abelian group of infinite order which leaves the differential equations of motion invariant. Solutions are developed in terms of elementary functions instead of elliptic or other higher transcendental functions and are shown to agree with known results.

Ramnath, R.↗

DOE OSTI2025

Parallel derivative-free optimization for simulation-based design of behind-the-meter energy systems

In this work, the integrated design and dispatch of behind-the-meter or distributed resources (e.g. stationary battery storage and solar PV generation) is considered. A simulation-based framework is employed, generating high-fidelity results with closed-loop predictive control at a fine resolution, at the expense of high computational cost (several minutes to a few hours per design point). To address this challenge, parallel derivative-free design methods are considered. Four methods are compared, including state-of-the-art surrogate-based methods (Radial-Basis Functions and Gaussian processes) and sampling strategies, an evolutionary-based method, and a simple sequential grid refinement method. As a case study, two types of design problem with increasing complexity are considered, namely, the design of behind-the-meter resources (three design variables) and the inclusion of grid capacity (four design variables). The second yields a constrained design problem for which violations can only be determined after solving the computationally expensive simulation. For the three-dimensional case, all methods present a good performance, achieving a solution within 1% of the optimum after the first iteration, with the sequential grid refinement exhibiting the fastest convergence and achieving the best final objective value. This indicates that the parallel evaluation of multiple sampling points may be more important than the choice of method for small decision spaces. For the four-dimensional constrained case, the Genetic Algorithm presents the best tradeoff between performance and computational effort, while the rough objective function terrain generated by constraint violation penalties reduces the performance of surrogate-based methods. Contour plots with flat regions indicate flexibility in the optimal design and highlight the importance of characterizing the solution space.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2020

Radiolytic degradation of formic acid and formate in aqueous solution: modeling the final stages of organic mineralization under advanced oxidation process conditions

The successful use of advanced oxidation processes to treat aqueous solutions containing undesirable organic species requires the degradation of these species to lower molecular weight, lower hazard compounds. Safe application of this technology requires a thorough understanding of the mechanisms of degradation. These oxidative transformations are mainly initiated by the reactions of reactive oxygen species, particularly hydroxyl radicals. These react with organic molecules to generate carbon-centered radicals. In the presence of dissolved oxygen, the carbon-centered radicals are next converted to peroxyl radicals, which then decay to lower molecular weight species by multiple mechanistic pathways. Formic acid and its conjugate base formate are the last stable chemical species produced immediately before the complete mineralization of any organic molecule undergoing oxidative degradation in aqueous solution. Once understood, the radical-induced chemistry of formic acid/formate under these conditions has wide applicability in all advanced oxidation technologies. To develop this quantitative knowledge, here we have performed a series of 60 Co gamma irradiation studies on aqueous formic acid/formate over different pH and solution conditions. The measured species concentration changes, as a function of applied dose, are compared with the predictions of a kinetic computer model constructed from literature reactions and reported rate coefficients. The excellent agreement found between the results and modeling gives confidence in the mechanism presented here and provide the first complete computer model for the radiolytic degradation of formic acid in water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Elucidating ion capture and transport mechanisms of Preyssler anions in aqueous solutions using biased MACE-accelerated MD simulations

Equilibrium and biased multi-atomic cluster expansion (MACE) accelerated molecular dynamics (MD) simulations in aqueous solutions are performed to investigate the ion capture and transport mechanisms of the {P 5 W 30 } Preyssler anion (PA) as the smallest representative member of the extended polyoxometalate (POM) family with an internal cavity. The unique interatomic interactions present in the internal cavity vs the exterior of PA are carefully investigated using equilibrium MACE MD simulations for two representative Na(H 2 O)@PA and Na@PA complexes in aqueous solutions. Our careful analyses of radial distribution functions and coordination numbers show that the presence of confined water in Na(H 2 O)@PA has profound modulating effects on the nature of the interactions of the encapsulated ion with the oxygens of the PA cavity. Using well-converged MACE-accelerated multiple walker well-tempered metadynamics simulations with nanosecond timescales, two different associative (ion exchange) and dissociative (ion ejection) ion transport mechanisms were carefully investigated for Na + as one of the most abundant and representative ions present in seawater and saline solutions. By comparing systems with and without confined water, it was found that the presence of only one pre-encapsulated confined water in Na(H 2 O)@PA dramatically changes the free energy landscape of ion transport processes. It was also found that the contraction and dilation of the two windows present in PA directly influence the Na + and H 2 O transport. Furthermore, the results from this work are helpful, as they show a viable path toward tuning the ion exchange and transport phenomena in aqueous solutions of POM molecular clusters and frameworks.

25 ENERGY STORAGE↗

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