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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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At least 289 records · Page 16

Surrogate Modeling of Nonlinear Dynamic Systems: A Comparative Study

Surrogate models play a vital role in overcoming the computational challenge in designing and analyzing nonlinear dynamic systems, especially in the presence of uncertainty. This paper presents a comparative study of different surrogate modeling techniques for nonlinear dynamic systems. Four surrogate modeling methods, namely, Gaussian process (GP) regression, a long short-term memory (LSTM) network, a convolutional neural network (CNN) with LSTM (CNN-LSTM), and a CNN with bidirectional LSTM (CNN-BLSTM), are studied and compared. All these model types can predict the future behavior of dynamic systems over long periods based on training data from relatively short periods. The multi-dimensional inputs of surrogate models are organized in a nonlinear autoregressive exogenous model (NARX) scheme to enable recursive prediction over long periods, where current predictions replace inputs from the previous time window. Three numerical examples, including one mathematical example and two nonlinear engineering analysis models, are used to compare the performance of the four surrogate modeling techniques. The results show that the GP-NARX surrogate model tends to have more stable performance than the other three deep learning (DL)-based methods for the three particular examples studied. The tuning effort of GP-NARX is also much lower than its deep learning-based counterparts.

42 ENGINEERING↗

Electronic structure prediction of multi-million atom systems through uncertainty quantification enabled transfer learning

The ground state electron density — obtainable using Kohn-Sham Density Functional Theory (KS-DFT) simulations — contains a wealth of material information, making its prediction via machine learning (ML) models attractive. However, the computational expense of KS-DFT scales cubically with system size which tends to stymie training data generation, making it difficult to develop quantifiably accurate ML models that are applicable across many scales and system configurations. Here, we address this fundamental challenge by employing transfer learning to leverage the multi-scale nature of the training data, while comprehensively sampling system configurations using thermalization. Our ML models are less reliant on heuristics, and being based on Bayesian neural networks, enable uncertainty quantification. We show that our models incur significantly lower data generation costs while allowing confident — and when verifiable, accurate — predictions for a wide variety of bulk systems well beyond training, including systems with defects, different alloy compositions, and at multi-million-atom scales. Moreover, such predictions can be carried out using only modest computational resources.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

OpenCHAMI Introduction: Cloud-like HPC Management for the Composable future [Slides]

OpenCHAMI is: An independent partnership of large HPC operators and vendor(s); Based on the APIs and Microservices from the Cray System Manager; A set of governance standards for developing HPC system management software aligned with cloud principles; A github organization; A set of software repositories in active development to enable sites to solve their own problems in a shareable way.

97 MATHEMATICS AND COMPUTING↗

Assembly and Repair of the Photosystem II Reaction Center

This project investigated the biochemical and biophysical mechanisms governing assembly and repair of Photosystem II (PSII), the membrane protein complex responsible for solar-driven water oxidation in oxygenic photosynthesis. The work focused on three integrated areas: (1) protein–protein interactions that facilitate PSII assembly in cyanobacterial biogenesis centers, (2) the chemical mechanism of photo-assembly of the Mn 4 CaO 5 oxygen-evolving complex (OEC), and (3) mechanisms that target PSII reaction centers for degradation and repair in photosynthetic organisms. Using electron paramagnetic resonance spectroscopy, protein biochemistry, molecular genetics, quantitative mass spectrometry, and computational modeling, the project demonstrated that proton release events limit early steps of OEC assembly and that chloride and calcium ions facilitate Mn oxidation and intermediate stabilization. Complementary studies identified chaperone recruitment mechanisms in cyanobacterial PSII biogenesis centers and translation and protease factors involved in PSII turnover in Chlamydomonas. Together, these results establish proton management and coordinated protein quality control as central design principles in PSII assembly and repair and provide mechanistic insight relevant to biological and artificial photosynthetic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient and robust phase-split computations in the internal energy, volume, and moles ( UVN ) space

Phase-split computations in an isolated system, which in general may be defined as one where the total internal energy (U), volume (V), and the number of moles (N = N 1 , N 2 ,..., N n ) of the components are fixed at some specified set of values, involves the determination of the temperature (T), pressure (P), plus the amount and composition of the various phases that constitute the system. A simpler, but analogous problem is one where T, P, and N are specified instead. In TPN space, one may first perform a stability analysis to determine whether the system is stable, meaning whether at equilibrium it will split up into multiple phases or remain in single phase. If the single-phase state is unstable, the stability analysis reliably provides a good set of initial guesses in the subsequent phase-split computations. In UVN space, however, we demonstrate that the stability analysis (which is the main subject of our earlier study [1]) may not in general provide good enough initial guesses; we offer alternative strategies for setting up good initial guesses. Furthermore, we show that a combination of successive substitution iteration (SSI) and Newton's method---two iterative methods that are prevalent in the literature in TPN space---facilitates a robust and efficient algorithm for phase-split computations in isolated systems. Finally, this combination has so far not been applied in UVN space.

02 PETROLEUM↗

Predicting Catalyst Surface Stability Under Reaction Conditions Using Deep Reinforcement Learning and Machine Learning Potentials

Catalysts are critical for most large-scale energy intensive chemical transformation processes, such as energy storage, liquid fuel production, and the formation of chemical building blocks. The catalyst composition, structure, and morphology impact the performance under reaction conditions and influences properties like activity and selectivity. Many industrial catalysts offer imperfect activity/selectivity, or contain expensive metals. Further, catalysts can deactivate over time as the morphology changes or harsh reactive environments alter the surface structure. Methods to automatically model and predict the kinetics of how catalyst surfaces will restructure would enable engineers to design around these challenges, improve performance, increase longevity. This project investigated a specific type of machine learning model, deep reinforcement learning, machine learning models to act as surrogates for the physical system, and compared the results of these approaches with a specialized high-throughput experimental synthesis and measurement platform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Site Carbon-Supported Metal-Oxo Complexes in Heterogeneous Catalysis: Structure, Reactivity, and Mechanism

When early transition metal complexes are molecularly grafted onto catalyst supports, well-defined, surface-bound species are created, which are highly active and selective single-site heterogeneous catalysts (SSHCs) for diverse chemical transformations. Further, in this minireview, we analyze and summarize a less conventional type of SSHC in which molybdenum dioxo species are grafted onto unusual carbon-unsaturated scaffolds, such as activated carbon, reduced graphene oxide, and carbon nanohorns. The choice of earth-abundant, low-toxicity, versatile metal constituents, and various carbon supports illustrates “catalyst by design” principles and yields insights into new catalytic systems of both academic and technological interest. Here, we summarize experimental and computational investigations of the bonding, electronic structure, reaction scope, and mechanistic pathways of these unusual catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Models for Single–Site Heterogeneous Catalysts on Carbon: MoO 2 Epoxidation Catalyst Anchored to a Fullerene

Single-site molybdenum dioxo catalysts, fullerenol/MoO 2 , are prepared via grafting precursor (DME)MoO 2 Cl 2 onto a highly polyhydroxylated fullerene (ful) and an isomerically-pure and well-defined fullerene (ful*). These catalyst structures are characterized by ICP-OES, XPS, XANES, EXAFS, DRIFT, Raman, and NMR spectroscopy, and DFT. Mo 3d 5/2 XPS and Mo K-edge XANES assign the oxidation state as Mo(VI). Mo EXAFS data fitting reveals two Mo=O double and two Mo–O single bonds at distances of 1.7 and 1.9 Å, respectively, while an Mo=O stretchingl mode is observed at ~950 cm –1 by DRIFT and Raman spectroscopy. These data align well with DFT computational results, supporting the proposed catalyst structure as Fullerene(-μ-O-) 2 M(=O) 2 . Additionally, DFT provides insight into the energetically favorable grafting sites for an isomerically pure fullerenol. The scope of fullerenol/MoO 2 mediated alkene epoxidation includes abiotic alkenes, natural occurring terpenes, and conjugated olefins. For cyclooctene the rate law is first-order in [Mo], near first order in [olefin] and zero-order in [t-butyl hydroperoxide]. A plausible reaction mechanism involves peroxide addition first and then cyclooctene addition directly across the peroxo bond forming the epoxide product, consistent with DFT computation. Overall, fullerenol/MoO 2 shows promise as a sustainable and structurally well-defined system with versatile catalytic activity and good epoxidation recyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Autonomous continuous flow reactor synthesis for scalable atom-precision

With new instrumentation design, robotics, and in-operando hyphenated analytical tool automation, the intelligent discovery of synthesis pathways is becoming feasible. It can potentially bridge the gap for the scale-up of new materials. In this article, we review current progress and describe a new system that uses an autonomous continuous flow chemistry framework to translate high-quality lead molecules and materials to quantities that can meet scalability demands. At the core is a continuous flow synthesis platform that can design its viable synthesis pathway to a particular molecule or material and then autonomously carry it out. This is realized by integrating: (1) A workflow/architecture for multimode chemical/materials characterization in-line. The in-line characterization modes are NMR, ESR, IR, Raman, UV-Vis, GC-MS, and HPLC, along with ex-situ modes for X-Ray and neutron scattering; (2) Integration for feedback/analysis/data storage of the control variables; (3) A core software stack that includes deep learning and reinforcement learning alongside quantum chemistry and molecular dynamics; (4) On-demand compute architectures that parse calculations to compute resources needed which include light-weight edge, mid-level edge (NVIDA DGX-2), and high-performance computing. We demonstrate preliminary results on how this autonomous reactor system can enhance our ability to deliver deuterated materials, copolymers, and site-substituted molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Structure and Dynamics in Geochemical Systems

Neutron scattering is a powerful tool to elucidate the structure and dynamics of systems that are important to geochemists, including ion association in complex aqueous solutions, solvent-exchange reactions at mineral–water interfaces, and reaction and transport of fluids in nanoporous materials. This article focusses on three techniques: neutron diffraction, which can reveal the atomic-level structure of aqueous solutions and solids; quasi-elastic neutron scattering, which measures the diffusional dynamics at mineral–water interfaces; and small-angle neutron scattering, which can show how properties of nanoporous systems change during gas, liquid, and solute imbibition and reaction. Furthermore, the usefulness and applicability of the experimental results are extended by rigorous comparison to computational simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deep Eutectic Solvents as Candidates for Lithium Isotope Enrichment

Nuclear fusion is a phenomenon that is well known within the nuclear physics community as a viable option for alternative energy as many natural gases and fossil fuels are phased out of commercial use. Deuterium and tritium fusion reactions are currently the leading candidates for nuclear fusion, with a major limiting factor being a means to produce tritium on an industrial scale. Lithium-6 is a well-known isotope that can produce tritium and helium following a fission reaction with a neutron. Unfortunately, the lithium-6 enrichment methods are limited to the COLEX process, which leaves behind an alarming amount of mercury waste as a potential environmental contaminant. Deep eutectic solvents are believed to be a potential alternative to lithium isotope separations due to the ease of generation, in addition to the minimum environmental waste generated when these solvents are employed. Previous studies have suggested that deep eutectic solvents are capable of separating lithium isotopes by utilizing a 2-thenoyltrifluoroacetone and trioctylphosphine oxide system that can biphasically react with a buffered solution containing lithium chloride. This system displays a separation factor of 1.068, which when compared to the 1.054 separation within the COLEX process, makes it a potential candidate for lithium-6/7 separation. Within this study, we investigate this system in comparison to two newly synthesized deep eutectic solvents and find that within these acetylacetone-based systems, little isotopic separation is observed. We investigate these systems both experimentally and computationally, showing the different lithium cation affinities, in addition to proposing how the electron-donating or -withdrawing nature can influence these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electric field stimulates production of highly conductive microbial OmcZ nanowires

Multifunctional living materials are attractive due to their powerful ability to self-repair and replicate. However, most natural materials lack electronic functionality. Here we show that an electric field, applied to electricity-producing Geobacter sulfurreducens biofilms, stimulates production of cytochrome OmcZ nanowires with 1,000-fold higher conductivity (30 S cm -1 ) and threefold higher stiffness (1.5 GPa) than the cytochrome OmcS nanowires that are important in natural environments. Using chemical imaging-based multimodal nanospectroscopy, we correlate protein structure with function and observe pH-induced conformational switching to β-sheets in individual nanowires, which increases their stiffness and conductivity by 100-fold due to enhanced π-stacking of heme groups; this was further confirmed by computational modeling and bulk spectroscopic studies. These nanowires can transduce mechanical and chemical stimuli into electrical signals to perform sensing, synthesis and energy production. Overall, these findings of biologically produced, highly conductive protein nanowires may help to guide the development of seamless, bidirectional interfaces between biological and electronic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing f -Element Separations with ADAAM-EH: The Impact of Phase Modifiers and a DGA Aqueous Complexant

Recent investigations have used a 2-ethylhexyl diamide amine (ADAAM-EH) for Am/Cm separations in combination with N,N,N ',N '-tetraethyldiglycolamide as an aqueous complexant to achieve an unprecedented separation factor of 41. The aim of this research effort is to understand the speciation of trivalent lanthanide (Ln) and actinide (An) ions in the organic phase of an ADAAM-EH extraction system, both with and without phase modifiers (PM) (1-octanol and tri-n-butyl phosphate (TBP)). Leveraging spectroscopic techniques in combination with distribution ratio measurements provides an understanding of organic phase f-element ligand complexation. In the absence of PM, Ln is extracted in a stoichiometric 1:1 [M(ADAAM-EH) 1 (NO 3 ) x (H 2 O) 1 ](NO 3 ) 3-x complex. The addition of 1-octanol at 20 vol % results in multiple species present. One of the species is the same as the no PM case, and the other species results in an increased -OH coordination to the inner sphere, potentially displacing some NO 3 . In the case of TBP, increasing concentration results in additional red-shifted bands in the UV-visible spectra, suggesting the complexation of additional ligands of either ADAAM-EH or TBP. Finally, the new system knowledge obtained by and spectroscopic experiments will provide benchmarking information for computational studies of the inner- and outer-sphere coordination environments of f-element cations and insights into ADAAM-EH adduct formation with PM, like 1-octanol and TBP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identification of Known and Novel Monomers for Poly(hydroxyurethanes) from Biobased Materials

Sourcing polymers from biobased materials is desirable for a transition to a more sustainable world. However, finding new monomers sourced from biobased molecules requires extensive experimental effort, due to the fact that most biomolecules lack the functional groups or properties needed to serve as a monomer in a particular polymeric system without chemical modification. In this work, we demonstrate a computational screening method to obtain monomers of a non-isocyanate polyurethane (NIPU), polyhydroxyurethane (PHU), from biomolecules. Our method generates candidate monomers from a list of 15 selected biobased starting molecules by performing chemical transformations that are standard to chemical catalysis and organic synthesis on these starting molecules and then screening the results for molecules with moieties that can be used as monomers for a PHU. Product molecules from two generations of reaction, a total number of 20,057, were analyzed automatically to identify molecules that have two or more epoxy or cyclic carbonate functional groups as candidates for further derivatization. These 21 candidate molecules were then subjected to another two generations of reaction, producing a set of 17,913 additional molecules. Further scrutiny of this set for desired functional groups characterizing PHUs and querying against the PubChem database was carried out, and 15 known molecules that are commercially available were identified, with the desirable features that they are predicted to be derived from biobased starting molecules in four or fewer steps. Moreover, molecule space generated from this process was primarily comprised of molecules that were not known to PubChem, indicating the framework also has the ability to generate novel candidate monomers that originate from biobased starting points.

36 MATERIALS SCIENCE↗

BEAM CORE: A Flexible Ecosystem for Freight, Demographics, and Vehicle Analysis

The Behavior, Energy, Autonomy, and Mobility Comprehensive Regional Evaluator (BEAM CORE) is an open-source, modular ecosystem of highly refined, agent-based modeling tools developed by Lawrence Berkeley National Laboratory and the National Laboratory of the Rockies. Organizations such as metropolitan planning organizations, agencies, and companies can use BEAM CORE to analyze freight movement and optimize logistics solutions, assess the impacts of emerging freight technologies or e-commerce trends, model dynamic population growth and evolution, and understand the drivers and impacts of electric vehicle adoption across households in a given region. Users can choose from a flexible suite of modeling modules according to their needs and priorities. The modules integrate with travel demand models to support enhanced analysis of diverse scenarios involving freight movement, vehicle technologies, and other key factors relevant to regional planning.

33 ADVANCED PROPULSION SYSTEMS↗

Summary Report Of The FY25 Computational Fluid Dynamics Verification And Validation Exercises In The Advanced Reactor Technologies - Gas-cooled Reactor Program

Verification and Validation (V&V) of numerical tools is critical for ensuring reasonable predictions during design, safety analysis, and licensing. Recent work in the Advanced Reactor Technologies - Gas-cooled Reactor (ART-GCR) program has focused on V&V of common Computational Fluid Dynamics (CFD) tools that are used within the Untied States. This report presents an update on these CFD V&V activities. These Generation IV Forum (GIF) Very High Temperature Reactor (VHTR) Computational Methods, Validation, and Benchmarking (CMVB) is an international organization dedicated to the verification and validation of High Temperature Gas-Cooled Reactor (HTGR) simulation tools. Participation in the CMVB provides additional value to the V&V activities, as it allows for access to a wider range of data, and provides valuable benchmarking exercises. Three HTGR phenomena are targeted: Reactor Cavity Cooling System (RCCS) performance, core bypass flow, and lower plenum mixing. Simulations of the University of Wisconsin-Madison (UW-Madison) RCCS facilities are performed with Reynolds Averaged Navier-Stokes (RANS) in StarCCM+. Results are compared for both forced and natural convection conditions, with both exhibiting good agreement with experimental measurements. The Idaho National Laboratory (INL) matched index of refraction (MIR) and Korean Atomic Energy Research Institute (KAERI) bypass flow expeirments are used to validation CFD predictions of bypass flow. Simulations are performed with RANS in StarCCM+ and with Large Eddy Simulation (LES) in NekRS. Finally, preliminary simulations of the Institute of Nuclear and New Energy Technology (INET) lower plenum mixing facilities are presented. Initial work has developed models with LES, RANS, and porous media models. These preliminary models are presented and compared to each other to gauge differences in predictions with each of the three methods.

and Benchmarking (CMVB)↗

Adaptive Phenotypic Plasticity Stabilizes Evolution in Fluctuating Environments

Fluctuating environmental conditions are ubiquitous in natural systems, and populations have evolved various strategies to cope with such fluctuations. The particular mechanisms that evolve profoundly influence subsequent evolutionary dynamics. One such mechanism is phenotypic plasticity, which is the ability of a single genotype to produce alternate phenotypes in an environmentally dependent context. Here, we use digital organisms (self-replicating computer programs) to investigate how adaptive phenotypic plasticity alters evolutionary dynamics and influences evolutionary outcomes in cyclically changing environments. Specifically, we examined the evolutionary histories of both plastic populations and non-plastic populations to ask: (1) Does adaptive plasticity promote or constrain evolutionary change? (2) Are plastic populations better able to evolve and then maintain novel traits? And (3), how does adaptive plasticity affect the potential for maladaptive alleles to accumulate in evolving genomes? We find that populations with adaptive phenotypic plasticity undergo less evolutionary change than non-plastic populations, which must rely on genetic variation from de novo mutations to continuously readapt to environmental fluctuations. Indeed, the non-plastic populations undergo more frequent selective sweeps and accumulate many more genetic changes. We find that the repeated selective sweeps in non-plastic populations drive the loss of beneficial traits and accumulation of maladaptive alleles, whereas phenotypic plasticity can stabilize populations against environmental fluctuations. This stabilization allows plastic populations to more easily retain novel adaptive traits than their non-plastic counterparts. In general, the evolution of adaptive phenotypic plasticity shifted evolutionary dynamics to be more similar to that of populations evolving in a static environment than to non-plastic populations evolving in an identical fluctuating environment. All natural environments subject populations to some form of change; our findings suggest that the stabilizing effect of phenotypic plasticity plays an important role in subsequent adaptive evolution.

54 ENVIRONMENTAL SCIENCES↗