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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 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Multitask Machine Learning of Collective Variables for Enhanced Sampling of Rare Events

Computing accurate reaction rates is a central challenge in computational chemistry and biology because of the high cost of free energy estimation with unbiased molecular dynamics. In this work, a data-driven machine learning algorithm is devised to learn collective variables with a multitask neural network, where a common upstream part reduces the high dimensionality of atomic configurations to a low dimensional latent space and separate downstream parts map the latent space to predictions of basin class labels and potential energies. Here, the resulting latent space is shown to be an effective low-dimensional representation, capturing the reaction progress and guiding effective umbrella sampling to obtain accurate free energy landscapes. This approach is successfully applied to model systems including a 5D Müller Brown model, a 5D three-well model, the alanine dipeptide in vacuum, and an Au(110) surface reconstruction unit reaction. It enables automated dimensionality reduction for energy controlled reactions in complex systems, offers a unified and data-efficient framework that can be trained with limited data, and outperforms single-task learning approaches, including autoencoders.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Small Sample Reactivity Measurements in the RRR/SEG Facility: Reanalysis using TRIPOLI-4

This work involved reanalyzing the RRR/SEG integral experiments performed at the Rossendorf facility in Germany throughout the 1970s and 80s. These small sample reactivity worth measurements were carried out using the pile oscillator technique for many different fission products, structural materials, and standards. The coupled fast-thermal system was designed such that the measurements would provide insight into elemental data, specifically the competing effects between neutron capture and scatter. Comparing the measured to calculated reactivity values can then provide adjustment criteria to ultimately improve nuclear data for fast reactor designs. Due to the extremely small reactivity effects measured (typically less than 1 pcm) and the specific heterogeneity of the core, the tool chosen for this analysis was TRIPOLI-4. This code allows for high fidelity 3-dimensional geometric modeling, and the most recent, unreleased version, is capable of exact perturbation theory.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
NASA NTRS1991

Experimental validation of docking and capture using space robotics testbeds

Docking concepts include capture, berthing, and docking. The definitions of these terms, consistent with AIAA, are as follows: (1) capture (grasping)--the use of a manipulator to make initial contact and attachment between transfer vehicle and a platform; (2) berthing--positioning of a transfer vehicle or payload into platform restraints using a manipulator; and (3) docking--propulsive mechanical connection between vehicle and platform. The combination of the capture and berthing operations is effectively the same as docking; i.e., capture (grasping) + berthing = docking. These concepts are discussed in terms of Martin Marietta's ability to develop validation methods using robotics testbeds.

Spofford, John↗
DOE OSTI2019

Subtask 1.4 - Techno-Economic Assessment of Regional Carbon Utilization Scenarios and Attendant Monitoring Technology

The U.S. Department of Energy (DOE) Carbon Storage Program seeks to develop technologies to significantly improve the effectiveness of carbon capture and storage (CCS), reduce the cost of implementation, and support the readiness of widespread commercial deployment by 2035. To accomplish this goal, technical and economic barriers must be addressed and the results used to inform regulators and industry on the safety, permanence, and viability of carbon storage. To help overcome these barriers, the Energy & Environmental Research Center (EERC) conducted three activities: 1) investigate the regional techno-economic life cycle of CO2 enhanced oil recovery (EOR) in North Dakota, 2) assist DOE in determining the prospective CO2 storage resource of residual oil zones (ROZs), and 3) develop a seismic technique for monitoring geologic storage of CO2. These three activities address two strategic goals enumerated in the DOE–EERC Cooperative Agreement, namely, 1) to advance foundational science and 2) to inform data-driven policies that enhance U.S. economic growth and job creation, energy security, and environmental quality. Activity 1 In North Dakota, there is synergistic incentive to develop and implement CO2 EOR technologies. Regional industry partners are actively seeking options that can cost-effectively improve the efficiency of power production, while also coproducing CO2 for use in EOR applications. A full-value-chain techno-economic assessment that links lignite resources, power generation, and EOR is needed to determine the implications for a state or region to continue to use these resources or look elsewhere for other energy sources and revenue streams. The integration of North Dakota’s lignite power industry with the state’s oil industry has the potential to revitalize legacy oil fields and produce up to 1 billion barrels of additional oil using CO2 EOR while providing a market for a CO2 commodity captured at coal-fired power plants. Revitalization of North Dakota’s legacy oil fields will bring new industry investment to the state, resulting in the growth of oil-related jobs and revenue through oil sales, severance tax, and associated oilfield development activities (drilling, pipelines, etc.). CO2 demand for EOR and incremental oil production were calculated for 201 conventional oil fields in North Dakota. Infrastructure development in the fields was estimated using 1) a traditional vertical well arrangement of CO2 injectors and oil producers and 2) an advanced case where horizontal wells were used exclusively. Pipeline, compression, and recycling infrastructure requirements were also estimated. When viewed from the CO2 capture and CO2 EOR sectors, the advanced case showed a positive investment scenario when including potential benefits of the 45Q tax credit policy. An economic evaluation of a full implementation of CO2 EOR showed an average $60 billion potential state economic impact estimated over the 37-year construction and production time frame could be realized with an assumed oil price of $65/bbl. Oil price ranges of $35–$90/bbl cause an estimated variation of ±$5 billion over the potential effort. The total net state government revenues were estimated over the 37-year construction and production time frame. With an assumed oil price of $65/bbl, total potential fiscal impact could average $7.4 billion. This result ranges about ±$2.5 billion for a potential EOR implementation effort for oil price ranges of $35–$90/bbl. This broad-brush assessment was focused on “magnitude-of-effect” perspectives of what CO2 capture and use for EOR could mean to the state. Whether CO2 EOR ever becomes widely adopted is not the issue at this stage of evaluation. The question being answered is, How valuable could CO2 capture and CO2 EOR be for the state and local jurisdictions in western North Dakota? The results of the current economic assessment remove any ambiguity to that question. Full implementation of CO2 EOR as modeled in this study provides substantial economic benefits to the state, even at low oil prices (i.e., $35/bbl). Job creation and government revenues could be substantial, depending on the scale of implementation. With a better understanding of what CO2 EOR might mean for the state’s economy, the focus can now shift to the policies and financial mechanisms needed to make private investment in CO2 capture and use as EOR competitive with other energy-related pursuits. Activity 2 ROZs contain remnants of oil not swept away by natural waterflooding. Although nearly all of the identified ROZs are found in West Texas, there is evidence that this category of oil reservoir can be found in other major oil-producing basins of the United States. Because the formation of these oil reservoirs is distinct from other conventional reservoirs, the method to estimate the prospective CO2 storage resource in ROZs may be equally distinct from the method used for conventional fields. As such, the EERC collaborated with DOE’s National Energy Technology Laboratory (NETL) to investigate the feasibility of CO2 storage in ROZs and determine what specific modification (if any) needs to be made to the current DOE volumetric method to estimate prospective CO2 storage resource in oil reservoirs. This activity built on a previous EERC investigation to identify ROZs in the Williston and Powder River Basins and upon collaborations between the EERC and NETL to develop storage resource estimation methods for different types of geologic CO2 storage. Review of the volumetric approach raised questions about the applicability of such an approach to hydrocarbon-bearing zones without the inclusion of potential hydrocarbon production. A production-based approach was presented by the EERC to inform the working group of additional methods of increasing the CO2 storage resource potential. Because the production-based method focuses more heavily on oil recovery than CO2 storage, it was not included in the working group manuscript. Activity 3 The EERC has used sparse and irregular seismic arrays to detect CO2 injected into a reservoir. The variability of seismic noise recorded by the sensors directly impacts the seismic interpretation. However, designing noise attenuation workflows effectively can be a more challenging task using sparse and irregular arrays for data acquisition. Based on the hypothesis that noncoherent noise is stationary during weekly data acquisition, a new machine-learning algorithm was developed to automatically estimate noise conditions using passive records, noise from active records, and ancillary information. The new noise attenuation processing workflow can improve the time-lapse detection of CO2 from sparse and irregular array acquisitions. Results show spatial and temporal noise patterns can be related to the location of the sensors and the weather conditions during the data acquisition and that our attenuation processing workflow can improve the time-lapse detection of CO2 from sparse and irregular array acquisitions. This effort was funded in part through the EERC–DOE Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by the North Dakota Department of Commerce.

Peck, Wesly↗
DOE OSTI2024

Advancing spatiotemporal forecasts of CO 2 plume migration using deep learning networks with transfer learning and interpretation analysis

Accurate and timely forecasts of CO 2 plume distribution throughout the injection and post-injection phases are crucial for detecting plume migration, assessing leakage risks, and supporting operational decisions in geologic carbon storage (GCS). Current convolutional neural network-based approaches primarily focus on spatial information and overlook temporal dependencies in plume distributions, thus limiting their ability to capture dynamic movement effects and provide accurate predictions of plume migration. In this work, we propose two deep learning models, Auto-Encoder (AE)-LSTM and Encoder-Decoder (ED)-ConvLSTM, each uniquely designed to capture both spatial and temporal features. We apply the proposed methods to forecast the dynamic distribution of CO 2 plumes based on 108 reservoir simulations over a 30-year injection and a 30-year post-injection period. The results indicate that the ED-ConvLSTM model outperforms the AE-LSTM model in accurately predicting the spatiotemporal dynamics of CO 2 plume migration, achieving R 2 values above 0.99. To provide a deeper understanding of these model predictions, we employ a gradient-based explanation method on the trained models. This approach provides insights into the influence of input variables on plume migration forecasts and uncovers the underlying prediction mechanisms of the proposed models. Furthermore, we introduce a transfer learning technique, enabling fast and accurate plume migration forecasting in the post-injection phase by leveraging the trained model during the injection phase. This reduces the necessity for extensive data collection or re-training. In conclusion, the methods proposed in our work enhances the performance and interpretability of CO 2 plume migration forecasts, thereby facilitating informed decision-making throughout the entire lifecycle of GCS applications.

58 GEOSCIENCES↗
NASA NTRS1977

New contributions to the problem of capture

Libration-point capture is analyzed in the framework of the restricted three-body problem in order to obtain general results capable of predicting the major features of an arbitrary postcapture orbit, with specific reference to capture as the presumed mode of origin of Jupiter's outer satellites. Some examples of libration-point capture are computed, the time a body remains captured is estimated, and a long-term numerical integration of orbits is carried out which shows that the equation used to estimate capture lifetimes is quite conservative. An extended capture criterion is proposed and used to demonstrate that direct postcapture orbits lie outside retrograde ones. Mass change involving one or both primaries is evaluated as a means of producing permanent capture, it is found that mass-change effects can produce 'pull-down capture', and consideration is given to the orbital evolution of Jupiter's outer satellites. The effect of drag in the solar nebula or in a nebula around proto-Jupiter on the capture process is briefly investigated. It is concluded that a capture origin for the outer satellites is improbable within the last 4.6 billion years but that either mass change or nebula drag could have been effective in producing capture.

Heppenheimer, T. A.↗
DOE OSTI2023

Chemical Feedback in the Self-Assembly and Function of Air–Liquid Interfaces: Insight into the Bottlenecks of CO 2 Direct Air Capture

As fossil fuels remain a major source of energy throughout the world, developing efficient negative emission technologies, such as direct air capture (DAC), which remove carbon dioxide (CO 2 ) from the air, becomes critical for mitigating climate change. Although all DAC processes involve CO 2 transport from air into a sorbent/solvent, through an air–solid or air–liquid interface, the fundamental roles the interfaces play in DAC remain poorly understood. In this work, we study the interfacial behavior of amino acid (AA) solvents used in DAC through a combination of vibrational sum frequency generation spectroscopy and molecular dynamics simulations. This study revealed that the absorption of atmospheric CO 2 has antagonistic effects on subsequent capture events that are driven by changes in bulk pH and specific ion effects that feedback on surface organization and interactions. Among the three AAs (leucine, valine, and phenylalanine) studied, we identify and separate behaviors from CO 2 loading, chemical changes, variations in pH, and specific ion effects that tune structural and chemical degrees of freedom at the air–aqueous interface. The fundamental mechanistic findings described here are anticipated to enable new approaches to DAC based on exploiting interfaces as a tool to address climate change.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Machine Learning-Accelerated First-Principles Molecular Dynamics Explains Anomalous Lattice Thermal Expansion in BaZr 0.78 Y 0.22 O 3-δ

Fuel cells are a vital clean energy technology that converts chemical energy directly into electricity with high efficiency, making them a cornerstone of a sustainable energy future. Herein we investigate the thermal and chemical lattice expansion behavior of hydrated BaZr 0.78 Y 0.22 O 3-δ using machine learning-accelerated ab initio molecular dynamics simulations. Here, our results reproduce the experimentally observed non-monotonic and anomalous temperature dependence of lattice expansion, which we attribute to the competing effects of thermal expansion and dehydration—two mechanisms that influence the lattice expansion in opposite directions. The importance of this work lies in its detailed demonstration of how advanced computational techniques can accurately capture complex environmental effects, providing a valuable framework for modeling similar phenomena in a variety of material systems and applications.

Proton conducting fuel cell↗
NASA NTRS1995

Micro-abrasion package capture cell experiment on the trailing edge of LDEF: Impactor chemistry and whipple bumper shield efficiencies

Four of the eight available double layer microparticle capture cells, flown as the experiment A0023 on the trailing (West) face of LDEF, have been extensively studied. An investigation of the chemistry of impactors has been made using SEM/EDX techniques and the effectiveness of the capture cells as bumper shields has also been examined. Studies of these capture cells gave positive EDX results, with 53 percent of impact sites indicating the presence of some chemical residues, the predominant residue identified as being silicon in varying quantities.

Fitzgerald, Howard J.↗
DOE OSTI2015

Lake Charles CCS Project (Final Technical Report, Phase 2)

In late September 2014 development of the Lake Charles Clean Energy (LCCE) Plant was abandoned resulting in termination of Lake Charles Carbon Capture and Sequestration (CCS) Project which was a subset the LCCE Plant. As a result, the project was only funded through Phase 2A (Design) and did not enter Phase 2B (Construction) or Phase 2C (Operations). This report was prepared relying on information prepared and provided by engineering companies which were engaged by Leucadia Energy, LLC to prepare or review Front End Engineering and Design (FEED) for the Lake Charles Clean Energy Project, which includes the Carbon Capture and Sequestration (CCS) Project in Lake Charles, Louisiana. The Lake Charles Carbon Capture and Sequestration (CCS) Project was to be a large-scale industrial CCS project intended to demonstrate advanced technologies that capture and sequester carbon dioxide (CO 2 ) emissions from industrial sources into underground formations. The Scope of work was divided into two discrete sections; 1) Capture and Compression prepared by the Recipient Leucadia Energy, LLC, and 2) Transport and Sequestration prepared by sub-Recipient Denbury Onshore, LLC. Capture and Compression-The Lake Charles CCS Project Final Technical Report describes the systems and equipment that would be necessary to capture CO 2 generated in a large industrial gasification process and sequester the CO 2 into underground formations. The purpose of each system is defined along with a description of its equipment and operation. Criteria for selection of major equipment are provided and ancillary utilities necessary for safe and reliable operation in compliance with environmental regulations are described. Construction considerations are described including a general arrangement of the CCS process units within the overall gasification project. A cost estimate is provided, delineated by system area with cost breakdown showing equipment, piping and materials, construction labor, engineering, and other costs. The CCS Project Final Technical Report is based on a Front End Engineering and Design (FEED) study prepared by SK E&C, completed in [June] 2014. Subsequently, Fluor Enterprises completed a FEED validation study in mid-September 2014. The design analyses indicated that the FEED package was sufficient and as expected. However, Fluor considered the construction risk based on a stick-build approach to be unacceptable, but construction risk would be substantially mitigated through utilization of modular construction where site labor and schedule uncertainty is minimized. Fluor’s estimate of the overall EPC project cost utilizing the revised construction plan was comparable to SKE&C’s value after reflecting Fluor’s assessment of project scope and risk characteristic. Development was halted upon conclusion of Phase 2A FEED and the project was not constructed.Transport and Sequestration – The overall objective of the pipeline project was to construct a pipeline to transport captured CO 2 from the Lake Charles Clean Energy project to the existing Denbury Green Line and then to the Hastings Field in Southeast Texas to demonstrate effective geologic sequestration of captured CO 2 through commercial EOR operations. The overall objective of the MVA portion of the project was to demonstrate effective geologic sequestration of captured CO 2 through commercial Enhanced Oil Recovery (EOR) operations in order to evaluate costs, operational processes and technical performance. The DOE target for the project was to capture and implement a research MVA program to demonstrate the sequestration through EOR of approximately one million tons of CO 2 per year as an integral component of commercial operations.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2021

Network Based Estimation of Wind Farm Power and Velocity Data Under Changing Wind Direction

This paper describes an estimation algorithm for velocity and power output signals in a wind farm under changing wind direction. A graph-theoretic definition describes the wind farm as a collection of nodes (turbines) and time-varying weighted edges (inter-turbine wake propagation) that change as a function of incoming wind direction. The velocity at each turbine is determined through a discrete input-output model. Changes in wind direction serve as the input and the output is defined in terms of a time-varying weighted adjacency matrix that depends on the time-delay of information propagation between turbines. These delays, which are defined in terms of the advection speed of the wind and the distance between the turbines, capture the delayed effect of wind direction changes on the inter-connectivity of the graph as the wind conditions at the farm inlet propagate through the turbine array. An event-based update framework is employed to capture time-dependent topology changes due to shifts in wind direction. Simulation results for dynamically changing wind inlet directions to a circular wind farm are compared to predictions from both the static and dynamic versions of the FLOw Redirection and Induction in Steady State (FLORIS) model. The approach is shown to enable real-time tracking of dynamic changes to wind farm power output within a framework that can be easily integrated into real-time, horizon-based, control strategies that typically do not account for wind direction changes.

distributed↗
DOE OSTI2022

Advanced Integrated Reticular Sorbent-Coated System to Capture CO 2 from the Atmosphere (AIR2CO2)

GE Research Center (GRC) and the University of California, Berkeley (UCB) executed an 15-month, $1.0 MM program to develop a lab-scale material system to extract CO 2 from ambient air using UCB’s pioneering sorbent technology and GRC’s composite coating expertise. The primary objective of this project was to develop an “Advanced Integrated Reticular Sorbent-Coated System to Capture CO 2 from the Atmosphere (AIR2CO2)” at a Technology Readiness Level (TRL) of 3. The AIR2CO2 concept relies on two key innovations: 1) advanced sorbent architectures with high capacity and rapid sorption kinetics that enable effective CO 2 capture at low concentrations, and 2) tailored MOF-binder slurry formulations and coating processes that enable sorbent integration into a novel additively-manufactured contactor.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Design and modeling of indirectly driven magnetized implosions on the NIF

The use of magnetic fields to improve the performance of hohlraum-driven implosions on the National Ignition Facility (NIF) is discussed. The focus is on magnetically insulated inertial confinement fusion, where the primary field effect is to reduce electron-thermal and alpha-particle loss from the compressed hotspot (magnetic pressure is of secondary importance). We summarize the requirements to achieve this state. The design of recent NIF magnetized hohlraum experiments is presented. These are close to earlier shots in the three-shock, high-adiabat (BigFoot) campaign, subject to the constraints that magnetized NIF targets must be fielded at room-temperature, and use ≲1 MJ of laser energy to avoid the risk of optics damage from stimulated Brillouin scattering. We present results from the original magnetized hohlraum platform, as well as a later variant that gives a higher hotspot temperature. In both platforms, imposed fields (at the capsule center) of up to 28 T increase the fusion yield and hotspot temperature. Integrated radiation-magneto-hydrodynamic modeling with the Lasnex code of these shots is shown, where laser power multipliers and a saturation clamp on cross-beam energy transfer are developed to match the time of peak capsule emission and the P2 Legendre moment of the hotspot x-ray image. The resulting fusion yield and ion temperature agree decently with the measured relative effects of the field, although the absolute simulated yields are higher than the data by 2.0−2.7×. The tuned parameters and yield discrepancy are comparable for experiments with and without an imposed field, indicating the model adequately captures the field effects. Self-generated and imposed fields are added sequentially to simulations of one BigFoot NIF shot to understand how they alter target dynamics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

A Micro-Mechanical Constitutive Model to Predict Hygrothermal Aging of Cross-Linked Polymers

Abstract A multi-physics material model is presented to describe the effects of temperature, oxygen, and humidity on the constitutive response of cross-linked polymers. The effect of hygrothermal damage on the mechanical integrity of the polymer matrix can be considered as the result of damage accumulation of two independent aging mechanism namely, i) thermo-oxidative, and ii) hydrolytic aging. In order to capture the mutual effects of thermo-oxidative and hydrolytic aging, an assumption has been made that each of the aging phenomenon can be superposed to each other. In fact, each of them works independently and as a result, they can compete with each other. Utilizing the theory of network decomposition, all phenomena and their correlation were modeled and thus, the strain energy function of the polymer matrix is written with respect to four independent mechanisms, i) the shrinking original matrix that has neither been attacked by water nor oxygen, ii) conversion of the first network to two new network due to the reduction and formation of cross-links, and iii) energy loss from network degradation due to attack of the water molecules to polymer active agents. Moreover, the proposed model is micro-mechanically based and is mainly relevant on thin samples due to our underlying assumption of homogeneous diffusion of oxygen and water throughout the matrix. The model has been validated against extensive data-sets obtained from experiments we specifically designed for concept validation.

Bahrololoumi, Amir↗
DOE OSTI2023

CO 2 capture from wet flue gas using a water-stable and cost-effective metal-organic framework

We report the use of MIL-120 as a water-stable and cost-effective metal-organic framework (MOF) for selectively capturing CO 2 from wet flue gas. Synthesized using inexpensive and environmentally benign reagents in water, MIL-120 possesses one-dimensional pores decorated with hydroxyl-bridged Al(III) ions and benzene rings with an interstitial spacing of 4.78 Å. Carbon dioxide isotherms show steep uptake at low pressure, and the affinity of MIL-120 for CO 2 is 44 kJ mol –1 . CO 2 -loading 13 C solid-state nuclear magnetic resonance and Fourier transform infrared spectra tracking the sorption of CO 2 into MIL-120 revealed that the interplay of pore size, functionality, and dimensionality is vital for CO 2 restriction within the pores of MIL-120. Breakthrough experiments reveal that MIL-120 can capture CO 2 from dry and wet flue gas with uptake capacities of 1.215 and 1.118 mmol g –1 , respectively. Our work highlights the synthetic benefits of MIL-120 and elucidates its selective capture of CO 2 from wet flue gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2010

CFD Fuel Slosh Modeling of Fluid-Structure Interaction in Spacecraft Propellant Tanks with Diaphragms

Liquid sloshing within spacecraft propellant tanks causes rapid energy dissipation at resonant modes, which can result in attitude destabilization of the vehicle. Identifying resonant slosh modes currently requires experimental testing and mechanical pendulum analogs to characterize the slosh dynamics. Computational Fluid Dynamics (CFD) techniques have recently been validated as an effective tool for simulating fuel slosh within free-surface propellant tanks. Propellant tanks often incorporate an internal flexible diaphragm to separate ullage and propellant which increases modeling complexity. A coupled fluid-structure CFD model is required to capture the damping effects of a flexible diaphragm on the propellant. ANSYS multidisciplinary engineering software employs a coupled solver for analyzing two-way Fluid Structure Interaction (FSI) cases such as the diaphragm propellant tank system. Slosh models generated by ANSYS software are validated by experimental lateral slosh test results. Accurate data correlation would produce an innovative technique for modeling fuel slosh within diaphragm tanks and provide an accurate and efficient tool for identifying resonant modes and the slosh dynamic response.

Sances, Dillon J.↗
DOE OSTI2022

Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO 2 in Water Catalyzed by Iron Porphyrins

Microenvironments tailored by multifunctional secondary coordination sphere groups can enhance catalytic performance at primary metal active sites in natural systems. In this work, we capture this biological concept in synthetic systems by developing a family of iron porphyrins decorated with imidazolium (im) pendants for the electrochemical CO 2 reduction reaction (CO 2 RR), which promotes multiple synergistic effects to enhance CO 2 RR and enables the disentangling of second-sphere contributions that stem from each type of interaction. Fe-ortho-im(H), which poises imidazolium units featuring both positive charge and hydrogen-bond capabilities proximal to the active iron center, increases CO 2 binding affinity by 25-fold and CO 2 RR activity by 2000-fold relative to the parent Fe tetraphenylporphyrin (Fe-TPP). Comparison with monofunctional analogs reveals that through-space charge effects have a greater impact on catalytic CO 2 RR performance compared to hydrogen bonding in this context.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electron-impact ionization from excited states method

We present a distorted-wave with exchange (DWE) formulation for computing electron-impact ionization (EII) cross sections within the recently developed excited states method (ESM) for plasmas. The ESM provides a self-consistent quantum-mechanical description of both bound and continuum electronic states in dense plasmas, incorporating finite-temperature and screening effects absent in isolated-atom approaches. Using this framework, we calculate EII cross sections for lithium across a wide range of temperatures and densities. We show that the ESM reproduces the isolated-atom limit at low densities while capturing strong plasma effects, such as pressure ionization and shape resonances, at solid density. Comparisons with isolated-atom DWE and average-atom (AA) calculations reveal that, although AA cross sections can approximate configuration average behavior, the ESM provides more accurate, state-resolved answers. In conclusion, these results demonstrate that the ESM allows one to obtain rate coefficients for collisional-radiative modeling of plasmas out of local thermodynamical equilibrium.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗