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At least 307 records · Page 17

The Strengths and Weaknesses of Logic Formalisms to Support Mishap Analysis

The increasing complexity of many safety critical systems poses new problems for mishap analysis. Techniques developed in the sixties and seventies cannot easily scale-up to analyze incidents involving tightly integrated software and hardware components. Similarly, the realization that many failures have systemic causes has widened the scope of many mishap investigations. Organizations, including NASA and the NTSB, have responded by starting research and training initiatives to ensure that their personnel are well equipped to meet these challenges. One strand of research has identified a range of mathematically based techniques that can be used to reason about the causes of complex, adverse events. The proponents of these techniques have argued that they can be used to formally prove that certain events created the necessary and sufficient causes for a mishap to occur. Mathematical proofs can reduce the bias that is often perceived to effect the interpretation of adverse events. Others have opposed the introduction of these techniques by identifying social and political aspects to incident investigation that cannot easily be reconciled with a logic-based approach. Traditional theorem proving mechanisms cannot accurately capture the wealth of inductive, deductive and statistical forms of inference that investigators routinely use in their analysis of adverse events. This paper summarizes some of the benefits that logics provide, describes their weaknesses, and proposes a number of directions for future research.

Johnson, C. W.↗

Proposed Critical Thinking Metrics for Power Grid Trainees

The TRS Intro to Critical Thinking for Operational Decision-Making course for power grid operators seeks to help trainees improve their use of critical thinking skills in operation environments. To determine the effectiveness of this training, we have identified 3 categories of evaluation measures: critical thinking metrics, situation awareness (SA) evaluations, and behavioral observations. Critical thinking metrics seek to directly measure trainee’s ability to use critical thinking skills through their verbalized responses to different questions or scenarios. SA will be evaluated during various points throughout simulated exercises completed during the training. SA evaluations aim to determine the level of a trainee’s ability to perceive, comprehend and anticipate events in the operational environment. This construct will be assessed through verbalized responses to questions informed by the Situation Awareness Global Assessment Technique (SAGAT). Behavioral observations capture how trainees use the system, including which simulator displays or windows they use or actions they perform and in what order. These observations help us understand how the critical thinking training may inform operator action. We hypothesize that while these measures are correlated with each other, they provide different perspectives on each trainee’s ability to gain SA and use critical thinking skills in operation environments. By comparing these measures in a pre-assessment and a post-assessment, we can determine how much improvement a trainee gains through the training. These measures may also be used during the training as appropriate. This document specifies these 3 categories of measures, which components of these measures currently seem to be the best candidates to use in the training course, and which parts of the training course is related to each component.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Domain architecture and catalysis of the Staphylococcus aureus fatty acid kinase

Fatty acid kinase (Fak) is a two-component enzyme that generates acyl-phosphate for phospholipid synthesis. Fak consists of a kinase domain protein (FakA) that phosphorylates a fatty acid enveloped by a fatty acid binding protein (FakB). The structural basis for FakB function has been established, but little is known about FakA. Here, we used limited proteolysis to define three separate FakA domains: the amino terminal FakA_N, the central FakA_L, and the carboxy terminal FakA_C. The isolated domains lack kinase activity, but activity is restored when FakA_N and FakA_L are present individually or connected as FakA_NL. The X-ray structure of the monomeric FakA_N captures the product complex with ADP and two Mg 2+ ions bound at the nucleotide site. The FakA_L domain encodes the dimerization interface along with conserved catalytic residues Cys240, His282, and His284. AlphaFold analysis of FakA_L predicts the catalytic residues are spatially clustered and pointing away from the dimerization surface. Furthermore, the X-ray structure of FakA_C shows that it consists of two subdomains that are structurally related to FakB. Analytical ultracentrifugation demonstrates that FakA_C binds FakB, and site-directed mutagenesis confirms that a positively charged wedge on FakB meshes with a negatively charged groove on FakA_C. Finally, small angle X-ray scattering analysis is consistent with freely rotating FakA_N and FakA_C domains tethered by flexible linkers to FakA_L. These data reveal specific roles for the three independently folded FakA protein domains in substrate binding and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The New National Vision for Space Exploration

From the Apollo landings on the Moon, to robotic surveys of the Sun and the planets, to the compelling images captured by advanced space telescopes, U.S. achievements in space have revolutionized humanity s view of the universe and have inspired Americans and people around the world. These achievements also have led to the development of technologies that have widespread applications to address problems on Earth. As the world enters the second century of powered flight, it is appropriate to articulate a new vision that will define and guide U.S. space exploration activities for the next several decades. Today, humanity has the potential to seek answers to the most fundamental questions posed about the existence of life beyond Earth. Telescopes have found planets around other stars. Robotic probes have identified potential resources on the Moon, and evidence of water - a key ingredient for life - has been found on Mars and the moons of Jupiter. Direct human experience in space has fundamentally altered our perspective of humanity and our place in the universe. Humans have the ability to respond to the unexpected developments inherent in space travel and possess unique skills that enhance discoveries. Just as Mercury, Gemini, and Apollo challenged a generation of Americans, a renewed U.S. space exploration program with a significant human component can inspire us - and our youth - to greater achievements on Earth and in space. The loss of Space Shuttles Challenger and Columbia and their crews are a stark reminder of the inherent risks of space flight and the severity of the challenges posed by space exploration. In preparation for future human exploration, we must advance our ability to live and work safely in space and, at the same time, develop the technologies to extend humanity s reach to the Moon, Mars, and beyond. The new technologies required for further space exploration also will improve the Nation s other space activities and may provide applications that could be used to address problems on Earth. Like the explorers of the past and the pioneers of flight in the last century, we cannot today identify all that we will gain from space exploration; we are confident, nonetheless, that the eventual return will be great. Like their efforts, the success of future U.S. space exploration will unfold over generations. The fundamental goal of this new national vision is to advance U.S. scientific, security, and economic interests through a robust space exploration program. In support of this goal, the United States will: 1) Implement a sustained and affordable human and robotic program to explore the solar system and beyond; 2) Extend human presence across the solar system, starting with a human return to the Moon by the year 2020, in preparation for human exploration of IMars and other destinations; 3) Develop the innovative technologies, knowledge, and infrastructures both to explore and to support decisions about the destinations for human exploration; and 4) Promote international and commercial participation in exploration to further U.S. scientific, security, and economic interests.

Sackheim, Robert L.↗

Understanding the effect of density functional choice and van der Waals treatment on predicting the binding configuration, loading, and stability of amine-grafted metal organic frameworks

Metal organic frameworks (MOFs) are crystalline, three-dimensional structures with high surface areas and tunable porosities. Made from metal nodes connected by organic linkers, the exact properties of a given MOF are determined by node and linker choice. MOFs hold promise for numerous applications, including gas capture and storage. M2(4,4′-dioxidobiphenyl-3,3′-dicarboxylate)—henceforth simply M2(dobpdc), with M = Mg, Mn, Fe, Co, Ni, Cu, or Zn—is regarded as one of the most promising structures for CO2 capture applications. Further modification of the MOF with diamines or tetramines can significantly boost gas species selectivity, a necessity for the ultra-dilute CO2 concentrations in the direct-air capture of CO2. There are countless potential diamines and tetramines, paving the way for a vast number of potential sorbents to be probed for CO2 adsorption properties. The number of amines and their configuration in the MOF pore are key drivers of CO2 adsorption capacity and kinetics, and so a validation of computational prediction of these quantities is required to suitably use computational methods in the discovery and screening of amine-functionalized sorbents. In this work, we study the predictive accuracy of density functional theory and related calculations on amine loading and configuration for one diamine and two tetramines. In particular, we explore the Perdew–Burke–Ernzerhof (PBE) functional and its formulation for solids (PBEsol) with and without the Grimme-D2 and Grimme-D3 pairwise corrections (PBE+D2/3 and PBEsol+D2/3), two revised PBE functionals with the Grimme-D2 and Grimme-D3 pairwise corrections (RPBE+D2/3 and revPBE+D2/3), and the nonlocal van der Waals correlation (vdW-DF2) functional. We also investigate a universal graph deep learning interatomic potential’s (M3GNet) predictive accuracy for loading and configuration. These results allow us to identify a useful screening procedure for configuration prediction that has a coarse component for quick evaluation and a higher accuracy component for detailed analysis. Our general observation is that the neural network-based potential can be used as a high-level and rapid screening tool, whereas PBEsol+D3 gives a completely qualitatively predictive picture across all systems studied, and can thus be used for high accuracy motif predictions. We close by briefly exploring the predictions of relative thermal stability for the different functionals and dispersion corrections.

Chemistry↗

Printable Spacecraft: Flexible Electronic Platforms for NASA Missions

Atmospheric confetti. Inchworm crawlers. Blankets of ground penetrating radar. These are some of the unique mission concepts which could be enabled by a printable spacecraft. Printed electronics technology offers enormous potential to transform the way NASA builds spacecraft. A printed spacecraft's low mass, volume and cost offer dramatic potential impacts to many missions. Network missions could increase from a few discrete measurements to tens of thousands of platforms improving areal density and system reliability. Printed platforms could be added to any prime mission as a low-cost, minimum resource secondary payload to augment the science return. For a small fraction of the mass and cost of a traditional lander, a Europa flagship mission might carry experimental printed surface platforms. An Enceladus Explorer could carry feather-light printed platforms to release into volcanic plumes to measure composition and impact energies. The ability to print circuits directly onto a variety of surfaces, opens the possibility of multi-functional structures and membranes such as "smart" solar sails and balloons. The inherent flexibility of a printed platform allows for in-situ re-configurability for aerodynamic control or mobility. Engineering telemetry of wheel/soil interactions are possible with a conformal printed sensor tape fit around a rover wheel. Environmental time history within a sample return canister could be recorded with a printed sensor array that fits flush to the interior of the canister. Phase One of the NIAC task entitled "Printable Spacecraft" investigated the viability of printed electronics technologies for creating multi-functional spacecraft platforms. Mission concepts and architectures that could be enhanced or enabled with this technology were explored. This final report captures the results and conclusions of the Phase One study. First, the report presents the approach taken in conducting the study and a mapping of results against the proposed Phase One objectives. Then an overview of the general field of printed electronics is provided, including manufacturing approaches, commercial drivers, and the current state of integrated systems. The bulk of the report contains the results and findings of Phase One organized into four sections: a survey of components required for a printable spacecraft, technology roadmaps considerations, science mission and engineering applications, and potential risks and challenges of the technology.

Spacecraft↗

Near-Zero Power MOF-Based Sensors for NO 2 Detection

Detection and capture of toxic nitrogen oxides (NO x ) is important for emissions control of exhaust gases and general public health. The ability to directly electrically detect trace (0.5–5 ppm) NO 2 by a metal–organic framework (MOF)-74-based sensor at relatively low temperatures (50 °C) is demonstrated via changes in electrical properties of M-MOF-74, M = Co, Mg, Ni. The magnitude of the change is ordered Ni > Co > Mg and explained by each variant's NO 2 adsorption capacity and specific chemical interaction. Ni-MOF-74 provides the highest sensitivity to NO 2 ; a 725× decrease in resistance at 5 ppm NO2 and detection limit <0.5 ppm, levels relevant for industry and public health. Furthermore, the Ni-MOF-74-based sensor is selective to NO 2 over N 2 , SO 2 , and air. Linking this fundamental research with future technologies, the high impedance of MOF-74 enables applications requiring a near-zero power sensor or dosimeter, with the active material drawing <15 pW for a macroscale device 35 mm 2 with 0.8 mg MOF-74. Finally, this represents a 10 4 –10 6 × decrease in power consumption compared to other MOF sensors and demonstrates the potential for MOFs as active components for long-lived, near-zero power chemical sensors in smart industrial systems and the internet of things.

47 OTHER INSTRUMENTATION↗

The Prediction of Jet Noise Ground Effects Using an Acoustic Analogy and a Tailored Green's Function

An assessment of an acoustic analogy for the mixing noise component of jet noise in the presence of an infinite surface is presented. The reflection of jet noise by the ground changes the distribution of acoustic energy and is characterized by constructive and destructive interference patterns. The equivalent sources are modeled based on the two-point cross- correlation of the turbulent velocity fluctuations and a steady Reynolds-Averaged Navier-Stokes (RANS) solution. Propagation effects, due to reflection by the surface and refaction by the jet shear layer, are taken into account by calculating the vector Green's function of the linearized Euler equations (LEE). The vector Green's function of the LEE is written in relation to Lilley's equation; that is, approximated with matched asymptotic solutions and the Green's function of the convective Helmholtz equation. The Green's function of the convective Helmholtz equation for an infinite flat plane with impedance is the Weyl-van der Pol equation. Predictions are compared with an unheated Mach 0.95 jet produced by a nozzle with an exit diameter of 0.3302 meters. Microphones are placed at various heights and distances from the nozzle exit in the peak jet noise direction above an acoustically hard and an asphalt surface. The predictions are shown to accurately capture jet noise ground effects that are characterized by constructive and destructive interference patterns in the mid- and far-field and capture overall trends in the near-field.

Miller, Steven A. E.↗

High-Temperature Modal Survey of a Hot-Structure Control Surface

NASA Dryden is directing a program to test a Carbon-Silicon Carbide (C/SiC) Ruddervator Subcomponent Test Article (RSTA). The RSTA is a truncated version of the full-scale X-37 hot-structure control surface incorporating all major features including the metallic spindle and five major C/SiC quasi isotropic lay-up components secured with C/SiC fasteners. As part of NASA's Aeronautics Research Mission Directorate Hypersonics program, the RSTA will undergo thermal-structural testing to develop an extensive database for future structural design and analysis methodology validation. Ground Vibration Tests (GVTs) are routinely conducted for model validation in supporting flutter analysis for subsonic and supersonic vehicles; however, for hypersonic vehicle applications, GVT techniques are not well-established. New fabrication technologies, high-temperature materials systems, and sensors offer new opportunities to develop techniques for performing GVTs at elevated temperatures. The RSTA is comprised of materials whose stiffness both increases and decreases with increasing temperature. The impact of this type of material system interaction must be understood as it will ultimately affect hypersonic flutter analysis. The test objectives are to perform room-temperature GVTs, develop the capability to conduct high-temperature GVTs and to compare and generate an understanding of the modal characteristics which capture RSTA's material interaction when subjected to temperature varying conditions.

Spivey, Natalie D.↗

Production, Outflow Velocity, and Radial Distribution of H2O and OH in the Coma of Comet C/1995 O1 [Hale-Bopp] from Wide Field Imaging of OH

Observations of OH are a useful proxy of the water production rate (Q(sub H2O)) and outflow velocity (V(sub out)) in comets. From wide field images taken on 03/28/1997 and 04/08/1997 that capture the entire scale length of the OH coma of comet C/1995 O1 (Hale-Bopp), we obtain Q(sub H2O) from the model-independent method of aperture summation. With an adaptive ring summation algorithm, we extract the radial brightness distribution of OH 0-0 band emission out to cometocentric distances of up to 10(exp 6) km, both as azimuthal averages and in quadrants covering different position angles relative to the comet-Sun line. These profiles are fit using both fixed and variable velocity 2-component spherical expansion models to estimate V(sub OH) with increasing distance from the nucleus. The OH coma of Hale-Bopp was more spatially extended than previous comets, and this extension is best matched by a variable acceleration of H2O and OH that acted across the entire coma, but was strongest within 1-2 x 10(exp 4) km from the nucleus. Our models indicate that V(sub OH) at the edge of our detectable field of view (10(exp 6) km) was approx. 2-3 times greater in Hale-Bopp than for a 1P/Halley-class comet at 1 AU, which is consistent with the results of more sophisticated gas-kinetic models, extrapolation from previous observations of OH in comets with Q(sub H2O) greater than 10(exp 29)/s , and direct radio measurements of the outer coma Hale-Bopp OH velocity. The most probable source of this acceleration is thermalization of the excess energy of dissociation of H2O and OH over an extended collisional coma. When the coma is broken down by quadrants in position angle, we find an azimuthal asymmetry in the radial distribution that is characterized by an increase in the spatial extent of OH in the region between the orbit-trailing and anti-sunward directions. Model fits specific to this area and comparison with radio OH measurements suggest greater acceleration here, with V(sub OH) approx. 1.5 times greater at a 10(exp 6) km cometocentric distance than elsewhere in the coma. We discuss several mechanisms that may have acted within the coma to produce the observed effect.

Harris, Walter M.↗

Fiber optic system for direct detection of CO 2 leakage in carbon storage wells (Abbreviated Final Report)

The feasibility study focused on the development of new fiber for distributed chemical sensing that will allow direct detection of CO2 leakages in the environment. This is particularly important for monitoring well integrity for carbon capture and storage (CSS), which can provide early warning for an incoming well failure and potential CO2 leaking through it. We proposed Raman or IR interrogation within gas-filled Holey Fibers (HoFs) interleaved with Fiber Bragg Grating (FBG) sections, so that the location and concentration of the gases would be provided simultaneously. The methodology would overcome current roadblocks to using fiber optics for CO2 (and other gases) detection in wells with direct in-situ measurements of concentration along with other important parameters such as temperature and pressure. We were able to assess commercially available IR/Raman hollow core fiber and demonstrated detection of CO2 through them in our controlled environment setups at various pressure conditions. We have also established the ability of drilling precisely with fs-lases side holes to enable penetration of CO2 into the hollow core fiber and reduce diffusion rates. Open joint collars were also explored with double functionality: to obtain splice to solid core fiber critical for field deployment and create gas ingress locations. Both diffusion-only and pressurized fiber system have been constructed following COMSOL based semi-hybrid optical /fluidodynamics models. FBGs have been identified and procured and characterized. Along the work we leveraged internal modeling/design, photonics/laser characterization, optical fiber fabrication, and AM lab capabilities to design, develop and test in-house components or assemblies. Our results indicate the potential of HoF for CO2 downhole direct detection.

25 ENERGY STORAGE↗

Empirical Comparison of Machine Learning Approaches for Black-Box Modeling of Power Conversion System Dynamics

Inverter-based resources are key components in modern power systems, but accurately modeling their complex behavior can be challenging. Standard, generic converter models often oversimplify inverter dynamics, leading to significant errors in predicting performance. In this work, we compare several data-driven machine learning (ML) approaches for inverter modeling, performing experiments on power conversion systems, systematically varying input conditions, and recording the resulting voltages and currents. The ML models were then trained on this measured data to capture the inverter's dynamic response and to predict the inverter's output current. A performance comparison between the four ML models under study is conducted, laying the foundation for future work on hardware implementation for real-time inference.

30 DIRECT ENERGY CONVERSION↗

3D printing of void-free glass monoliths: rheological and geometric considerations

Direct ink writing (DIW) is a versatile additive manufacturing technique capable of printing 3D architectures from a broad range of materials. The key advantage of DIW is the ability to spatially control both the architecture and the composition of the printed part, which enables the production of components with previously unachievable combinations of functionalities. One emergent application space for DIW has been in additively manufactured glass optics, where a “green body” is patterned layer-by-layer by extruding a silica-based slurry through a microfluidic nozzle and then thermally consolidated to transparent glass. A critical aspect of the process is ensuring that the printed part is completely free of voids that can occur in the interstitial spaces between the extruded filaments. This outcome is governed by the interplay between ink rheology and strains imposed by the printing process and geometric packing of the filaments. Here, we explore the strain- and rate-dependent deformation events in the DIW process to determine conditions that enable the printing of void-free monoliths without sacrificing shape fidelity. We focus on yield stress fluids consisting of fumed silica nanoparticles dispersed in organic solvents at varied volume fractions to control the rheological properties. We investigate the printability of these ink materials as a function of print process variables and devise the appropriate dimensionless parameters that capture the geometry-dependent and rate-dependent effects on the deformation of the extruded ink. Lastly, we use these scaling arguments to construct a phase diagram for void-free monolith printability.

36 MATERIALS SCIENCE↗

STEREO and Wind Observations of Intense Cyclotron Harmonic Waves at the Earth's Bow Shock and Inside the Magnetosheath

We present the first observations of electron cyclotron harmonic waves at the Earth's bow shock from STEREO and Wind burst waveform captures. These waves are observed at magnetic field gradients at a variety of shock geometries ranging from quasi-parallel to nearly perpendicular along with whistler mode waves, ion acoustic waves, and electrostatic solitary waves. Large amplitude cyclotron harmonic waveforms are also observed in the magnetosheath in association with magnetic field gradients convected past the bow shock. Amplitudes of the cyclotron harmonic waves range from a few tens to more than 500 millivolts/meter peak-peak. A comparison between the short (15 meters) and long (100 meters) Wind spin plane antennas shows a similar response at low harmonics and a stronger response on the short antenna at higher harmonics. This indicates that wavelengths are not significantly larger than 100 meters, consistent with the electron cyclotron radius. Waveforms are broadband and polarizations are distinctively comma-shaped with significant power both perpendicular and parallel to the magnetic field. Harmonics tend to be more prominent in the perpendicular directions. These observations indicate that the waves consist of a combination of perpendicular Bernstein waves and field-aligned waves without harmonics. A likely source is the electron cyclotron drift instability which is a coupling between Bernstein and ion acoustic waves. These waves are the most common type of high-frequency wave seen by STEREO during bow shock crossings and magnetosheath traversals and our observations suggest that they are an important component of the high-frequency turbulent spectrum in these regions.

bow shock↗

Toward a persistent event-streaming system for high-performance computing applications

High-performance computing (HPC) applications have traditionally relied on parallel file systems and file transfer services to manage data movement and storage. Alternative approaches have been proposed that use direct communications between application components, trading persistence and fault tolerance for speed. Event-driven architectures, as popularized in enterprise contexts, present a compelling middle ground, avoiding the performance cost and API constraints of parallel file systems while retaining persistence and offering impedance matching between application components. However, adapting streaming frameworks to HPC workloads requires addressing challenges unique to HPC systems. This paper investigates the potential for a streaming framework designed for HPC infrastructures and use cases. We introduce Mofka, a persistent event-streaming framework designed specifically for HPC environments. Mofka combines the capabilities of a traditional streaming service with optimizations tailored to the HPC context, such as support for massively multicore nodes, efficient scaling for large producer-consumer workflows, RDMA-enabled high-performance network communications, specialized network fabrics with multiple links per node, and efficient handling of large scientific data payloads. Built using the Mochi suite of HPC data service components, Mofka provides a lightweight, modular, and high-performance solution for persistent streaming in HPC systems. We present the architecture of Mofka and evaluate its performance against Kafka and Redpanda using benchmarks on diverse platforms, including Argonne's Polaris and Oak Ridge's Frontier supercomputers, showing up to 8× improvement in throughput in some scenarios. We then demonstrate its utility in several real-world applications: a tomographic reconstruction pipeline, a workflow for the discovery of metal-organic frameworks for carbon capture, and the instrumentation of Dask workflows for provenance tracking and performance analysis.

HPC↗

Transformational Solid Oxide Fuel Cell (SOFC) Technology

This project was conducted under the Co-operative Agreement No. DE-FE0027584 with the US Department Energy to developed advanced Solid Oxide Fuel Cell (SOFC) Technologies. The overall objective of this project was to advance SOFC technology at the cell and stack level to enhance cell robustness and durability, increase performance, and reduce balance-of-plant (BOP) requirements. By reducing system complexity combined with the increases in power density and efficiency, the ultimate goal of the project was to increased reliability and to reduce capital and operating costs of installed systems. The project was focused on pathways that will reduce the cost of the SOFC cell and stack, including the following areas: Robust, redox tolerant cell technology Lower cost cell manufacturing through advances in cell design, which will reduce the amount of material, energy and time used in the fabrication of SOFCs High performance, low temperature electrolyte based on improvement of established materials Innovative SOFC stack architecture which truly integrates Balance of Plant functionality into the stack level design Thermal management of the fuel cell stack for increased durability and expanded window of operation Novel stack design amenable for use in sub-MW to multi-MW-scale power plants and having low replacement cost The incorporation of balance-of-plant (BOP) equipment into the stack platform increased the economic viability of smaller scale systems. The project objectives were met by a multi-prong approach, including new cell design complemented with modifications to existing cell technology, as well as a new stack design incorporating components typically included in the BOP, such as heat exchangers, oxidizer, fuel reformers, and recycle systems. The project culminated with demonstration of a stack test validating the viability of the cell and stack improvements. A cost model was also developed to estimate costs for the advanced stack technology at high volume manufacturing levels. The net outcome of the project is SOFC cell and stack technology with costs significantly below current DOE targets without compromising and, in some cases, improving on the performance and degradation rate demonstrated with the current state-of-the-art stack design. The results of this project advanced the reliability, robustness, and endurance of low-cost SOFC technology that ultimately are ready to be deployed in coal power systems with greater than 60 percent efficiency (based on higher heating value of fuel) and the capability for ≥97% CO 2 capture at a cost-of-electricity that is approximately 40 percent below presently available Integrated Gasification Combined Cycle systems.

03 NATURAL GAS↗

Role of Intermolecular Interactions in Deep Eutectic Solvents for CO 2 Capture: Vibrational Spectroscopy and Quantum Chemical Studies

Recent research and reviews on CO 2 capture methods, along with advancements in industry, have highlighted high costs and energy-intensive nature as the primary limitations of conventional direct air capture and storage (DACS) methods. In response to these challenges, deep eutectic solvents (DESs) have emerged as promising absorbents due to their scalability, selectivity, and lower environmental impact compared to other absorbents. However, the molecular origins of their enhanced thermal stability and selectivity for DAC applications have not been explored before. Therefore, the current study focuses on a comprehensive investigation into the molecular interactions within an alkaline DES composed of potassium hydroxide (KOH) and ethylene glycol (EG). Combining Fourier transform infrared (FT-IR) and quantum chemical calculations, the study reports structural changes and intermolecular interactions induced in EG upon addition of KOH and its implications on CO 2 capture. Experimental and computational spectroscopic studies confirm the presence of noncovalent interactions (hydrogen bonds) within both EG and the KOH-EG system and point to the aggregation of ions at higher KOH concentrations. Additionally, molecular electrostatic potential (MESP) surface analysis, natural bond orbital (NBO) analysis, quantum theory of atoms-in-molecules (QTAIM) analysis, and reduced density gradient-noncovalent interaction (RDG-NCI) plot analysis elucidate changes in polarizability, charge distribution, hydrogen bond types, noncovalent interactions, and interaction strengths, respectively. Evaluation of explicit and hybrid models assesses their effectiveness in representing intermolecular interactions. This research enhances our understanding of molecular interactions in the KOH-EG system, which are essential for both the absorption and desorption of CO 2 . The study also aids in predicting and selecting DES components, optimizing their ratios with salts, and fine-tuning the properties of similar solvents and salts for enhanced CO 2 capture efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Importance of finite-size corrections for accurate ab initio modeling of carrier capture at semiconductor defects: A case study of substitutional C N in GaN

In ab initio studies of carrier-capture processes in defective semiconductor materials, the single-effective-mode formalism and the static-coupling approximation have become the predominant theoretical approaches for determining carrier-capture coefficients. The single-mode formalism relies on accurate nonequilibrium defect energies obtained from density-functional theory (DFT), where required inputs are a series of configurationally displaced, defect-containing supercells obtained using an interpolative ansatz, and where the DFT outputs are corresponding total energies that have traditionally been postprocessed using a long-established ground-state formulation of finite-size corrections and defect-formation energies. This formulation remains commonly used even though the defects that form a configuration-coordinate (CC) diagram typically exist as structures that are displaced from the ground state. To remedy this inconsistency, Kumagai has recently proposed novel methods for implementing finite-size corrections specifically intended for DFT calculations of the defect energies used to construct CC diagrams and implement the single-mode formalism [Y. Kumagai, Phys. Rev. B 107, L220101 (2023)]. Kumagai's approach builds on the latest finite-size-correction methods introduced to describe vertical charge-state transitions for charge-localizing point defects in semiconductors and insulators [T. Gake et al., Phys. Rev. B 101, 020102 (2020); S. Falletta et al., Phys. Rev. B 102, 041115 (2020)]. The newly identified finite-size artifact treated in these studies is the polarization charge induced on a configurationally frozen defect and its subsequent interaction with a vertical transition in charge state. In this work, we evaluate Kumagai's proposed methodology by applying it in a high-precision DFT study of carrier capture by substitutional C N in GaN, a well-characterized and technologically relevant defect and material. We have rigorously calculated C N defect energies across various supercell sizes for each defect configuration and charge state on the hole-capture CC diagram of C N (𝑞=−1), enabling a direct comparison of the slopes of the defect energies versus inverse cell size with those predicted by Kumagai. The most consequential prediction of Kumagai's method is that these slopes distinctly vary as the square of the linear-interpolation parameter used to construct the nonequilibrium defect configurations. Our results quantitatively support this prediction. Moreover, with these new finite-size corrections and multiple-cell-size DFT calculations in place, we find that the classical energy barrier for hole capture by C N (𝑞=−1) in GaN decreases to 0.092–0.127 eV. This finding confirms the recent ≈ 0.1 eV prediction of Reshchikov based on the weak temperature dependence for hole capture observed in photoluminescence experiments [M. A. Reshchikov, J. Appl. Phys. 129, 121101 (2021)]. These results stand in stark contrast to previously calculated barriers of 0.486 and 0.73 eV, which also used the single-mode formalism but were obtained by instead using ground-state-based finite-size corrections. Our reduced classical barrier for capture increases the temperature-dependent hole-capture coefficient of a C N (𝑞=−1) defect by more than two to four orders of magnitude for temperatures of 100–600 K, compared to the previous 0.486 eV results. While other defects may not be as dramatically affected as here, we suggest that incorporating proper finite-size corrections for the vertical-transition-like states embedded within CC diagrams is an essential, yet previously unrecognized, component of accurate modeling of carrier-capture when using the single-effective-mode formalism.

dielectric properties↗