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At least 415 records · Page 23

Equally high efficiencies of organic solar cells processed from different solvents reveal key factors for morphology control

The power conversion efficiency of organic solar cells (OSCs) is exceeding 20%, an advance in which morphology optimization has played a significant role. It is generally accepted that the processing solvent (or solvent mixture) can help optimize morphology, impacting the OSC efficiency. Here we develop OSCs that show strong tolerance to a range of processing solvents, with all devices delivering high power conversion efficiencies around 19%. By investigating the solution states, the film formation dynamics and the characteristics of the processed films both experimentally and computationally, we identify the key factors that control morphology, that is, the interactions between the side chains of the acceptor materials and the solvent as well as the interactions between the donor and acceptor materials. Our work provides new understanding on the long-standing question of morphology control and effective guides to design OSC materials towards practical applications, where green solvents are required for large-scale processing.

14 SOLAR ENERGY↗

Develop a new integrated macro→micro←nano (MMN) multiscale modeling framework to optimize high strength aluminum alloys and processes for vehicle light-weighting​

Bending tests provide a means to study plane strain fracture performance of 6000 series aluminum alloys. Metrics from bending tests have been correlated with self-pierce riveting (SPR) performance of a high strength AA6111 automotive aluminum alloy in previous works. Using the ORNL HPC resources, this project developed an innovative macro→micro←nano (MMN) multiscale microstructure-based finite element (FE) code to further understanding of the relationship between microstructure and fracture properties of high-strength 6000-series alloys. This work started with microstructural characterization in both mesoscale and nanoscale and bending performance characterization of AA6111 HS2-T6 alloy at Ford, the MMN framework was applied to this alloy to simulate 3-point VDA bending. From the results of the macro-modeling of 3-point VDA bending, the critical region of fracture was identified, and the region geometry was used to construct the micro-model. The fracture criterion of micron-scale precipitates and aluminum matrix which contains submicron and nano particles (AL-SMP-NP) in the micro-model was calibrated and validated by comparing simulated and measured bending results. With the AL-SMP-NP fracture strain obtained, the fracture strain of Al-matrix containing nano particles (ALNP) will similarly be determined by a submicron scale-model using an edge-constrained FE modeling approach developed by Hu et al. With the ALNP fracture strain obtained, the fracture strain of Al-matrix containing no particles will similarly be determined by a nano scale-model using an edge-constrained FE modeling approach. After the MMN framework is built and fracture criterion calibrated, nano-model FE simulations with virtual microstructures was performed to obtain a reduced order model (ROM) of the fracture criterion of the ALNP as a function of volume fraction, size, and distribution of the nanoparticle. This nano→submicron→micro modeling part allows exploration of the influence of different material nanostructures from different process conditions on the bending properties within the multiscale bending simulation framework and the ROM of material bendability as a function of nanoparticle size and shape was established. This obtained reduced order model (ROM) could help guide the design and selection of materials to improve existing SPR process models that could replace trial-and-error rivet/die selection and help to design new rivet/die combinations capable of robustly joining new higher strength 6000 5 series alloys in automotive body structures. This would enable lightweighting of Ford vehicles leading to greater fuel efficiency and reduce manufacturing time and energy.

36 MATERIALS SCIENCE↗

Nondestructive Analysis of Commercial Batteries

Electrochemical batteries play a crucial role for powering portable electronics, electric vehicles, large-scale electric grids, and future electric aircraft. However, key performance metrics such as energy density, charging speed, lifespan, and safety raise significant consumer concerns. Enhancing battery performance hinges on a deep understanding of their operational and degradation mechanisms, from material composition and electrode structure to large-scale pack integration, necessitating advanced characterization methods. These methods not only enable improved battery performance but also facilitate early detection of substandard or potentially hazardous batteries before they cause serious incidents. Here, this review comprehensively examines the operational principles, applications, challenges, and prospects of cutting-edge characterization techniques for commercial batteries, with a specific focus on in situ and operando methodologies. Furthermore, it explores how these powerful tools have elucidated the operational and degradation mechanisms of commercial batteries. By bridging the gap between advanced characterization techniques and commercial battery technologies, this review aims to guide the design of more sophisticated experiments and models for studying battery degradation and enhancement.

36 MATERIALS SCIENCE↗

Expansion of Hazards and Probabilistic Risk Assessments of a Light-Water Reactor Coupled with Electrolysis Hydrogen Production Plants

This report builds upon the body of work sponsored by the Department of Energy (DOE) Light-Water Reactor Sustainability (LWRS) Flexible Power Operation and Generation (FPOG) program that presented generic probabilistic risk assessments (PRAs) for the addition of a heat extraction system (HES) to light-water reactors to support the co-location of a high temperature hydrogen electrolysis facility (HTEF). Probabilistic and deterministic hazards assessments and risk analyses are leveraged throughout this report. Several improvements and new analyses are included in this report. First, higher amounts of detail in the specifications of the generic HTEFs are used to produce scaled results for a 100, 500, and 1000 MW nominal hydrogen production facility. An additional hazard assessment of 1000 kg of hydrogen storage is performed. The facility hazards and footprint are assessed to determine the safe distance required for placement near the nuclear power plant (NPP). Second, specific designs for corresponding HESs for the different levels of support required by the HTEFs are analyzed in the PRA model. Third, a hazards analysis of the specified HTEFs leads not only to effects of the quantified risk assessment for the NPP, but also qualitative hazards assessment for the community. Finally, a seismic analysis and a high winds analysis have each been added to the PRA. The results investigate the applicability of the potential licensing approaches which do not require a full United States (U.S.) Nuclear Regulatory Commission (NRC) licensing review. The PRAs are generic and include listed assumptions. The HTEF design built for this project has further eliminated many conservative assumptions from the prior PRAs in this series. The PRA results indicate that the 10 CFR 50.59 licensing approach is justified due to the minimal increase in initiating event frequencies for all design basis accidents, with none exceeding 7.7%. The PRA results for core damage frequency and large early release frequency support the use of NRC Regulation Guide 1.174 as further risk information that supports a change without a full licensing amendment review. The hazard analyses and PRA confirm the need for engineered blast barriers of storage tanks and the common production header leaving the HTEF. The hazards analyses and PRA also confirm with high confidence that using the assumptions of design in this report that the safety case for licensing an HES addition and an HTEF sited with its unprotected high-pressure stage components 187 meters from the NPP’s transmission towers (the most fragile structure, system, and component) is strong.

08 HYDROGEN↗

Packaged Combined Heat and Power Technology Overview and Market Profile

Combined heat and power (CHP), sometimes referred to as cogeneration, is an efficient and clean approach to generating electric power and useful thermal energy onsite from a single fuel source, offering reliable and affordable energy services to businesses and institutions. Furthermore, CHP provides a cost effective opportunity to improve the environmental footprint and resilience of industrial and commercial facilities across the United States. CHP equipment can be custom-engineered or installed as a predesigned and assembled package. A packaged CHP system is a standardized, pre-engineered system that includes all equipment, piping, wiring, and ancillary components to deliver electricity and thermal energy to a host facility with minimal onsite engineering and design time. Packaged CHP systems can be shipped as single or multiple modules with standard interconnections (e.g., fuel; electrical; thermal—hot water, steam, and/or chilled water), which simplifies installation and reduces the costs associated with the project. Most containerized or single packaged CHP system offerings range from 10 kW to 3 MW in capacity. Packaged CHP systems are extending the operating, efficiency, and emissions benefits of CHP to nontraditional markets in commercial, institutional, multifamily, light manufacturing, government, and military applications. These markets tend to be served by smaller systems (less than 5 MW) that are conducive to pre-engineered packaging and/or modularization. Many of these sectors have limited CHP experience and technical resources to adequately evaluate, install, and maintain onsite CHP systems. The introduction of packaged CHP offerings from experienced CHP Packagers and Solution Providers has accelerated CHP adoption, lowered energy costs, reduced emissions, and strengthened energy resilience in these sectors. In 2019, the US Department of Energy (DOE) launched the Packaged CHP eCatalog to promote increased acceptance of efficient, cost-effective CHP in these applications. The Packaged CHP eCatalog is a web-based, searchable platform that hosts DOE-recognized packaged CHP systems with features designed to reduce economic and performance risks for designers, developers, owners, and facility operators interested in installing CHP. DOE established the Packaged CHP Accelerator at the same time to help launch and publicize the eCatalog, and to validate project performance, cost, and installation time of CHP packages across a variety of applications. Accelerator efforts documented installed cost reductions and installation time reductions of more than 20% for packaged CHP systems over 100 kW compared with custom-engineered systems. The Packaged CHP Accelerator and eCatalog established a peer-to-peer network connecting public and private sector partners including utilities, state energy offices, and energy efficiency program administrators interested in promoting cost-effective, efficient CHP systems, Packagers, and Solution Providers. Feedback from these partners, along with input from DOE’s CHP Technical Assistance Partnerships (CHP TAPs), was critical in understanding the current market for packaged CHP technologies, stimulating investment in these technologies, and guiding future directions for packaged CHP systems and their applications. This report provides background on packaged CHP systems, an overview of their benefits, a profile of current packaged CHP installations, and a summary of future market trends; this report is intended for facility owners, project developers, engineers, policymakers, and other stakeholders looking to increase the adoption of efficient, flexible, and resilient packaged CHP systems.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Nuclear Safety [Vol. 32, No. 4, October-December 1991]

Nuclear Safety is a review journal that covers significant developments in the field of nuclear safety. Its scope includes the analysis and control of hazards associated with nuclear energy, operations involving fissionable materials, and the products of nuclear fission and their effects on the environment. Primary emphasis is on safety in reactor design, construction, and operation; however, the safety aspects of the entire fuel cycle, including fuel fabrication, spent-fuel processing, nuclear waste disposal, handling of radioisotopes, and environmental effects of these operations, are also treated. Table of Contents for this issue follows. GENERAL SAFETY CONSIDERATIONS: 477 Report on the International Symposium on the Use of Probabilistic Safety Assessment for Operational Safety—PSA '91, S. Chakraborty and M. Khatib-Rahbar; 488 Good Relationships Are Pivotal in Nuclear Data Bases, A. S. Heger and B. V. Koen; 494 Technical Note: The Interagency Nuclear Safety Review Panel's Evaluation of the Ulysses Space Mission, J. A. Sholtis, Jr., D. A. Huff, L. B. Gray, N. P. Klug, and R. O. Winchester; ACCIDENT ANALYSIS: 502 The Severe Accident Analysis Program for the Savannah River Nuclear Production Reactors, M. L. Hyder; CONTROL AND INSTRUMENTATION: 511 A Framework for Selecting Suitable Control Technologies for Nuclear Power Plant Systems, R. A. Kisner; DESIGN FEATURES: 521 Containments for Gas-Cooled Power Reactors History and Status, P.W. Williams; ENVIRONMENTAL EFFECTS: 537 Indoor Radon: A Natural Risk, N. H. Harley and J.H. Harley; On the Importance of the Atmospheric Parameters in the Fission Products Distribution of a Severe Reactor Accident, M. C. Barla and A. R. Bayulken; Book Review: Health Effects of Exposure to Low Levels of Ionizing Radiation BEIR V, C. R. Richmond; WASTE AND SPENT FUEL MANAGEMENT: 555 Activities Related to Waste and Spent Fuel Management, M. D. Muhlheim and E. G. Silver OPERATING EXPERIENCES: 567 Effects of Component Aging on the Westhinghouse Control Rod Drive System, K. Sullivan and W. Gunther; 577 Reactor Shutdown Experience, Compiled by J. W. Cletcher, 580 Selected Safety-Related Events, Compiled by G. A. Murphy; 582 Operating U 8 Power Reactors, Compiled by M. D. Muhlheim and E. G. Silver, RECENT DEVELOPMENTS: 596 General Administrative Activities, Compiled by M. D. Muhlheim and E. G. Silver; 610 Reports, Standards, and Safety Guides, D. S. Queener; 614 Proposed Rule Changes as of June 30, 1991; ANNOUNCEMENTS: 520 Workshop on PC PRAISE: A Probabilistic Fracture Mechanics Personal Computer Code for Nuclear Power Plant Piping Reliability Assessment; 536 Fifth Workshop on Nuclear Power Plant Containment Integrity; 624 New OECD "International Information System on Occupational Exposure (ISOE)"; 625 Harvard School of Public Health Announces Short Courses; 625 Eighth Power Plant Dynamics, Control and Testing Symposium; 626 Second Training Course on Off-Site Emergency Planning and Response for Nuclear Accidents; 618 The Authors; 622 Reviewers of Nuclear Safety, Vol 32.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Autonomous System Inference, Trojan, and Adversarial Reprogramming Attack and Defense (Final)

In the world of ever-advancing technology, Autonomous Systems (AS) find extensive application, bolstering functionalities of critical infrastructures such as nuclear power plants. These systems, however, are increasingly becoming a target for nefarious activities, namely through inference attacks, trojan attacks, and adversarial reprogramming. This paper delves into a comprehensive exploration of machine learning (ML)-driven autonomous control systems within advanced nuclear reactor designs, revealing the vulnerabilities and proposing strategies for defense against potential cyber-attacks. Advanced cyber-attacks against critical infrastructure and the energy sector are becoming more common. With the invention of autonomous control systems (ACS) within advanced nuclear reactor designs, system designers, reactor operators, and regulators must consider cybersecurity during the design and operational phases. This article provides a cyber threat assessment of machine learning (ML)- based digital twinning (DT) technologies in the context of advanced reactor ACS. A cyber-physical testbed was created to emulate nuclear reactor digital instrumentation and controls (I&C) and act as a basis for the ACS. The ACS was designed as two plant-level DTs predicting reactor malfunctions and determining control actions and two component-level DTs responsible for classifying component states and forecasting component inputs and outputs (I/O). Two duplicate ACS designs– one using a traditional ML framework and one using an automated ML (AutoML) framework– were created and tested against cyber-attacks on training data, real-time process data, and ML model architectures to determine their respective qualitative cyber-risk in terms of likelihood and impact. Both frameworks showed similar cyber-resilience against training, real-time, and ML architecture attacks, proving that neither is inherently more secure. Recommended safeguard and security measures are posed to system designers, reactor operators, and regulators to maintain the cybersecurity of ML-based DT technologies such as ACS, prompting a holistic view of shared responsibility for maintaining cyber-secure ML-based systems. As global reliance on generation III reactors begins to be critically assessed, the evolution towards advanced reactor systems utilizing digital instrumentation and controls (I&C) becomes not merely preferable, but essential. The integration of semi and fully autonomous control systems (ACS), powered by digital I&C and machine learning (ML)-based digital twinning (DT) technologies, emerges as a potent strategy to mitigate operations and maintenance costs, thereby enhancing the economic feasibility of novel reactor designs. However, with a staggering 500% and 380% increase in cyber-attacks reported against the energy sector by the United States Department of Energy (DoE) and the European Union respectively, a surge in cyber vulnerabilities specifically targeting the nuclear industry has been 2 markedly observed. Notable incidents, such as the W32.Ramnit spyware infiltration at the Gundremmingen nuclear power plant in Germany and the Dtrack spyware intrusion at the Kudankulam nuclear power plant in India, while not directly compromising core industrial control systems (ICS), underscore a compelling necessity to fortify cybersecurity protocols in safeguarding reactor systems against increasingly adept digital adversaries. In light of this, our investigation extends beyond conventional cybersecurity parameters, diving into the intricate web of potential vulnerabilities woven into ML-based DTs and ACS in advanced reactor systems. A crafted cyber-physical testbed and preliminary ACS were devised to act as a mirror, reflecting potential configurations of advanced reactor control designs. Moreover, this study is intertwined with a scrutinization of ML models, developed either through conventional, manually tuned methodologies or via automated means through AutoML, probing into their cyber-risk profiles within operational technology (OT) environments. Expanding on this, two distinct ACS blueprints were forged – one navigating through the corridors of traditional ML and the other traversing the path of AutoML – in an effort to holistically encapsulate the considerations pivotal to ML-based DT control system design. Employing the SANS Institute Industrial Control System (ICS) Kill Chain and the MITRE ATT&CK Tactics, Techniques, and Procedures (TTP) framework, a structured analysis was conducted, launching three targeted attacks against the training dataset, real-time dataset, and ML models, therein dissecting the potential cyber-attack implications against both ML frameworks within an ACS milieu. It is essential to note that three distinct categories of attacks were conducted against both ACS configurations, each encompassing three distinct ML-based DTs, cumulating in a total of 18 varied attacks. This exploration extends into the realms of Autonomous System Inference, Trojan, and Adversarial Reprogramming Attack and Defense, unraveling vulnerabilities, and opportunities for fortified defenses against such intrusions, particularly where ML-driven technologies, and by extension, ACS, are deployed. Final recommendations, articulated through a lens of security, safeguard, and implementation considerations, are presented for both traditional and AutoML models, anchoring upon the existing knowledge landscape and ML-based DT modeling for ACS, and are offered as a beacon to guide the nuclear industry through the intricate cybersecurity challenges that lie ahead.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Ion energy distribution in an electron beam ion trap inferred from simulations of the trapped ion cloud

For this work, we have inferred the energy distribution of trapped ions in an electron beam ion trap (EBIT) from simulations of the spatial distribution of Fe 13+ ions and a comparison with measured visible light images of the ion cloud. We simulated the cloud of Fe 13+ ions by computing ion trajectories in the EBIT for different ion energy distributions used to initialize the trajectories. We then performed a least-squares fit to infer the ion energy distribution that best reproduced the measured ion cloud. These best-fit distributions were typically non-Maxwellian. For electron beam energies of 395–475 eV and electron beam currents of 1–9 mA, we find that the average ion energy is in the range of 10–300 eV. We also find that the average ion energy increases with increasing beam current approximately as $\langle$E$\rangle$ ≈ 25 I e eV, where I e is the electron beam current in mA. We have also compared our results to Maxwell-Boltzmann-distribution ion clouds. We find that our best-fit non-thermal distributions have an $\langle$E$\rangle$ that is less than half that of the T from the best-fit Maxwell-Boltzmann distributions ($\langle$E$\rangle$/q)/T=0.41 ± 0.05.

74 ATOMIC AND MOLECULAR PHYSICS↗

Structural and electronic changes in L⁢i 2 ⁢Ru⁢O 3 induced by lithium intercalation

Despite extensive research on oxide battery cathodes that transcend classical cationic redox activity, the detailed interplay between structural transformations and electronic redox processes remains insufficiently understood. We report a detailed study of the sequential structural and electronic changes in Li 2 RuO 3 upon lithium intercalation, characterized by powder x-ray and neutron diffraction alongside Ru and O K-edge x-ray absorption spectroscopy (XAS), and guided by operando synchrotron x-ray diffraction. During delithiation, Li 2 RuO 3 evolves from a well-defined monoclinic state to a complex trigonal phase via multiple intermediate structures, marked by significant changes in Ru-O bond distances that closely track the transition from a classical cationic redox to an unconventional process centered at oxygen states. Armed with high-quality atomic structural descriptions, computational models of the O K-edge XAS closely reproduce the experimentally observed spectral shifts. Lastly, we relate observations of electrochemical hysteresis with concurrent changes in the pathways of structural and electronic transitions. In conclusion, our results not only clarify the mechanisms underpinning voltage hysteresis in a model for lattice oxygen redox but also underscore the importance of structural fidelity in modeling redox behavior when this type of complex reactivity is present.

Li, Haifeng [Univ. of Illinois, Chicago, IL (Unite↗

Enhanced Selectivity for C 2 H 4 Production from C 2 H 6 on Partially Chlorinated IrO 2 (110) Surfaces

Modifying metal oxide surfaces to limit their oxidizing activity can provide a means of improving catalytic selectivity toward the partial oxidation of light alkanes. Here, in this study, we investigated the oxidation of C 2 H 6 on Cl-modified IrO 2 (110) surfaces using temperature-programmed reaction spectroscopy (TPRS) and first-principles microkinetic modeling. We find that substituting Cl for O in the IrO 2 (110) surface enhances the selectivity for C 2 H 6 conversion to C 2 H 4 during TPRS by suppressing extensive oxidation to CO x products, while also either enhancing C 2 H 4 production or altering it to a lesser extent, depending on the initial C 2 H 6 coverage. The C 2 H 4 selectivity increased with increasing C 2 H 6 and Cl coverage, but reached a limiting value below 50%. The Cl coverage changed negligibly during C 2 H 6 oxidation, and the surface reactivity decreased only marginally for Cl coverages up to 0.5 ML (monolayer). TPRS simulations using a microkinetic model predict C 2 H 4 and CO x product yields as a function of the Cl coverage that agree closely with the experimental results. According to the simulations, C 2 H 6 conversion to C 2 H 4 occurs on Cl-IrO 2 (110) by the hydrogenation of C 2 H 3 * species adsorbed in blocked states, in which neighboring sites are occupied only by unreactive HO and Cl species. The microkinetic modeling shows that H-hopping away from surface HO groups provides a relatively efficient route for C 2 H 3 * to escape blocked configurations and dehydrogenate, and that this process can limit the C 2 H 4 selectivity on Cl-IrO 2 (110) under the conditions studied. Overall, our results demonstrate that Cl-substitution into IrO 2 (110) enhances the selectivity for C 2 H 4 production from C 2 H 6 and provides insights into the reaction mechanism that can guide strategies to further improve the C 2 H 4 selectivity.

IrO2↗

Competitive Adsorption of NH 3 and H 2 O in Metal–Organic Framework Materials: MOF-74

Elucidating the interaction between coadsorbed H 2 O and NH 3 in metal–organic frameworks (MOFs) is of paramount importance to uncover mechanistic details of their competitive coadsorption behavior as well as to guide the design of new materials for enhanced NH 3 adsorption in humid environments. Nevertheless, molecular competition between NH 3 and H 2 O within the confined nanopores of MOFs was rarely explored and is poorly understood due to challenges in characterization. Here, we combine in situ infrared spectroscopy with ab initio calculations to unveil the competition of NH 3 and H 2 O for occupying active adsorption sites in the representative MOF-74 material by analyzing the kinetics and energetics of the molecular exchange process. We find that at a high NH 3 /H 2 O ratio, the incoming NH 3 is capable of displacing metal-bound H 2 O and moving it to secondary adsorption sites due to the stronger binding of NH 3 compared with H 2 O. Interestingly, the reverse process of H 2 O displacing metal-bound NH 3 is also possible upon increasing water concentration. Our calculations show that H 2 O exchanging the preabsorbed NH 3 at the metal site is driven not only by a reduced kinetic barrier but also by a favorable energetical state resulting from the formation of water clusters at metal sites and intermolecular H-bonding between the metal-coordinated H 2 O and displaced NH 3 . Our finding emphasizes that the description of molecular occupation in MOFs at equilibrium cannot simply be established by comparing molecules’ binding energies at their strongest binding sites derived by single-component measurements; rather, intermolecular interactions can greatly affect molecular distribution at equilibrium. Furthermore, we show that vibrational modes of adsorbed NH 3 are markedly perturbed upon contact with water molecules, accompanied by a large frequency shift (>30 cm –1 ) and considerable intensity decrease, which arises from the freezing of NH 3 vibrations by coadsorbed H 2 O. As a result, the mechanistic insight obtained through our study sheds light on molecular coadsorption processes in MOFs and helps to assess NH 3 removal efficiency of MOFs containing open-metal sites under realistic conditions, particularly in the presence of humidity.

36 MATERIALS SCIENCE↗

Exciton-Phonon Coupling and Carrier Relaxation in PbS Quantum Dots: The Case of Carboxylate Ligands

Some ligand-nanocrystal combinations exhibit rapid cooling of highly excited electronic states while other nanocrystal/shell combinations do not appear to have this effect. There remains a need to identify the distinguishing properties of ligand-nanocrystal interactions that avoid such rapid relaxation processes to guide the design of colloidal quantum dots (QDs) that take advantage of multiple exciton generation or hot-carrier extraction processes. Here, we use mid-infrared transient absorption spectroscopy to investigate the influence that carboxylate ligands with distinct excited state surface chemistries has on exciton-phonon coupling and hot exciton relaxation in PbS quantum dot (QD) films. Our findings reveal that despite significant differences in the excited state surface chemistry of oleate (OA) and iodide/mercaptopropionic acid (I-/MPA) ligands, PbS QD films passivated with both ligand types exhibit identical electronic relaxation rates and exciton-phonon coupling strengths within experimental precision. The data suggest that the inorganic lattice is the principal source of exciton-phonon coupling that influences hot exciton relaxation, rather than the vibronic modes of carboxylate ligands. The size-dependent nature of the exciton-phonon coupling strength is consistent with the localization of charge on the QD surfaces, which enhances the mixing of electronic and nuclear coordinates particularly when the electronic states are more quantum confined in smaller nanocrystals.

14 SOLAR ENERGY↗

Optimizing the impacts of solid additives on the operational stability and processing reliability of organic solar cells

Previous reports have revealed that by leveraging solid additives, organic solar cells (OSCs) can surpass the device’s performance beyond the intrinsic limitations of host photoactive molecules, a remarkable advancement. However, the impacts of more complex interactions introduced by solid additives are not yet well understood. Herein, optimizing the fabrication process based on the traditional efficiency-guided approach fails to represent the ideal and most practical devices. In particular, achieving superior operational stability while minimizing the device performance scattering was found to require processing solvent evaporation to be synchronized with the volatility of the chosen solid additive. However, this may be challenging since most organic photoactive materials display excellent efficiencies only with selected solvents. Accordingly, this work also demonstrates the potential of dual and complementary solvents selection, consisting of low boiling point (primary) and high boiling point (secondary). This strategy allows for the suppression of any potential trade-offs in efficiency. Meanwhile, the operational stability and precision of device performance are substantially enhanced. Additionally, solid additives have demonstrated that the singlet exciton dissociation rate does not limit the free charge generation yield. Finally, these findings are expected to reformulate OSC device fabrication strategies towards more practical devices.

36 MATERIALS SCIENCE↗

Electric Field Analysis in a Cold-Ion Source Using Stark Spectroscopy of Rydberg Atoms

Here, we analyze electric fields in ion sources generated by quasicontinuous photoionization of cold Rb atoms trapped in the focal spot of a near-concentric, in-vacuum cavity for 1064-nm laser light. Ion streams are extracted with an external electric field, F. Stark effects of Rb 57F and of nearby high-angular-momentum Rydberg levels, which exhibit large, linear Stark shifts, are employed to study the net electric-field probability distribution within the ion-source region over an extraction-field range of 0 < F < 0.35 V/cm. For F = 0, we also investigate ion-field-induced Stark spectra of the 60P 1/2 state, which exhibits a (lesser) quadratic electric-field response that affords a simplified electric-field analysis. Experimental Rydberg spectra are compared with theoretical Stark spectra, which are weighted with net electric-field distributions obtained from classical ion-trajectory simulations that include Coulomb interactions. Experiments and models are in good agreement. At small F and high ion-source rates, the field approximately follows a Holtsmark distribution, and the ion streams are degraded by the Coulomb microfields. With increasing F and at lower ion-source rates, the fields become narrowly distributed around F, resulting in directional ion streams that are less degraded by microfields. Our results are of interest for monitoring cold-ion sources for focused-ion-beam applications, where Coulomb interactions are of concern, and for studies of electric fields in cold plasmas.

74 ATOMIC AND MOLECULAR PHYSICS↗

Deciphering the Solvation Structure of Aqueous ZnCl 2 Solutions from X-ray Absorption Spectra Using the Interpretable Graph Neural Network

Machine learning (ML) provides powerful pathways for predicting spectroscopic observables from atomic structures, but its broader impact depends on making model predictions interpretable in terms of physical and chemical principles. Here, we introduce a physics-guided graph neural network (GNN) model that predicts Zn K-edge X-ray spectroscopy (XAS) spectra of aqueous ZnCl 2 solutions. Training data are generated from ab initio XAS calculations on molecular dynamics snapshots obtained using a machine learning interatomic potential. The GNN reproduces experimental spectra across concentrations from dilute (<0.1 m) to highly concentrated (30 m, “water-in-salt”) regimes and scales efficiently to large, disordered liquid systems beyond the reach of conventional ab initio approaches. Gradient-based attribution analysis reveals that the model learns physically meaningful structure-spectrum relationships. Ligand-specific attributions reflect orbital hybridization patterns and the origin of the excitations derived from the density functional theory. Bond-length attributions recover spectral shifts consistent with multiple-scattering theory. Finally, this work bridges data-driven prediction with electronic-structure theory, establishing a general paradigm for interpretable ML that links atomic structure, electronic structure, and spectroscopic observables.

25 ENERGY STORAGE↗

Multinuclear Solid-State NMR and NMR Crystallography of Solid Forms of Creatine and Creatinine

Creatine is a performance-enhancing supplement with two widely available commercial solid forms, namely, creatine monohydrate (creatine·H 2 O) and creatine HCl, the latter of which does not have a reported crystal structure. Moreover, commercial formulations of creatine may contain creatinine, an undesired impurity phase resulting from the self-cyclization of creatine during manufacturing. Therefore, reliable methods for characterizing the different solid forms of creatine and detecting the presence of creatinine are essential. Herein, we address these challenges using 13 C, 15 N, and 35 Cl solid-state NMR (SSNMR) spectroscopy to obtain distinct spectral fingerprints for creatine·H 2 O and creatine HCl, along with creatinine and creatinine HCl. The acquisition of these SSNMR spectra offers a robust approach for both the rapid characterization of each solid form and the detection of the impurity phases. Additionally, quadrupolar NMR crystallography-guided crystal structure prediction (QNMRX-CSP) was applied for the de novo crystal structure determination of creatine HCl, which was validated by the subsequently determined single-crystal X-ray diffraction (SCXRD) structure. Finally, to investigate the relationship between NMR parameters and structural features, 13 C and 15 N chemical shifts and 35 Cl electric field gradient (EFG) tensors were computed from geometry-optimized structures of the four solid forms by using dispersion-corrected DFT-D2* methods. Finally, this integrative approach offers a powerful framework for advancing the structural understanding and quality control of creatine-based supplements and next-generation formulations, as well as a wide range of other solid pharmaceuticals and nutraceuticals.

NMR↗

Physics-guided dual implicit neural representations for source separation

Significant challenges exist in efficient data analysis of most advanced experimental and observational techniques because the collected signals often include unwanted contributions, such as background and signal distortions, that can obscure the physically relevant information of interest. To address this, we have developed a self-supervised machine-learning approach for source separation using a dual implicit neural representation framework that jointly trains two neural networks: one for approximating distortions of the physical signal of interest and the other for learning the effective background contribution. Our method learns directly from the raw data by minimizing a reconstruction-based loss function without requiring labeled data or pre-defined dictionaries. We demonstrate the effectiveness of our framework by considering a challenging case study involving large-scale simulated, as well as experimental, momentum-energy-dependent inelastic neutron scattering data in a four-dimensional parameter space, characterized by heterogeneous background contributions and unknown distortions to the target signal. The method is found to successfully separate physically meaningful signals from a complex or structured background even when the signal characteristics vary across all four dimensions of the parameter space. An analytical approach that informs the choice of the regularization parameter is presented. Our method offers a versatile framework for addressing source separation problems across diverse domains, ranging from superimposed signals in astronomical measurements to structural features in biomedical image reconstructions.

47 OTHER INSTRUMENTATION↗

Nanoscopic strain evolution in single-crystal battery positive electrodes

Single-crystal Ni-rich layered oxides (SC-NMC) with a grain-boundary-free configuration have effectively addressed the long-standing cracking issue of conventional polycrystalline Ni-rich materials (PC-NMC) in lithium-ion batteries, prompting a shift in optimization strategies. However, continued reliance on anisotropic lattice volume change—a well-established failure indicator in PC-NMC—as a metric for understanding strain and guiding compositional design for SC-NMC becomes controversial. Here, in this study, by leveraging multiscale diagnostic techniques, we unravelled the distinct nanoscopic strain evolution in SC-NMC during battery operation, challenging the conventional composition-driven strategies and mechanical degradation indicators used for PC-NMC. Through particle-level chemomechanical analysis, we reveal a decoupling between mechanical stability and lattice volume change in SC-NMC, identifying that structural instability in SC materials is primarily driven by multidimensional lattice distortions induced by kinetics-driven reaction heterogeneity and progressively deactivating chemical phases. Using this mechanical failure mode, we redefine the roles of cobalt and manganese in maintaining mechanical stability. Unlike cobalt’s detrimental role in PC-NMC, we find cobalt to be critical in enhancing the longevity of SC-NMC by mitigating localized strain along the extended diffusion pathway, whereas manganese exacerbates mechanical degradation.

36 MATERIALS SCIENCE↗