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At least 199 records · Page 11

Understanding Process–Structure Relationships during Lamination of Halide Perovskite Interfaces

Fabrication of halide perovskite (HP) solar cells typically involves the sequential deposition of multiple layers to create a device stack, which is limited by the thermal and chemical incompatibility of top contact layers with the underlying HP semiconductor. One emerging strategy to overcome these restrictions on material selection and processing conditions is lamination, where two half-stacks are independently processed and then diffusion bonded to complete the device. Lamination reduces the processing constraints on the top side of the solar cell to allow new device designs, expanded use of deposition methods, and self-encapsulation of devices. While laminated perovskite solar cells with high efficiencies and novel interlayer combinations have been demonstrated, there is a limited understanding of how the lamination process parameters affect the diffusion-bond quality and material properties of the resulting HP layer. In this study, we systematically vary temperature, pressure, and time during lamination and quantify the resulting impacts on bonded area, grain domain size, and photoluminescence. A design of experiments is performed, and statistical analysis of the experimental results is used to quantitatively evaluate the resulting process–structure–property relationships. The lamination temperature is found to be the key parameter controlling these properties. Furthermore, a temperature of 150 °C enables successful bonding over 95% of the substrate area and also results in increases in apparent grain domain size and photoluminescence intensity. Based on these insights, the lamination temperature of functional perovskite solar cell devices is varied, demonstrating the importance of the resulting bond quality on device performance metrics.

14 SOLAR ENERGY↗

High-resolution analogue of time-domain phonon spectroscopy in the transmission electron microscope

Femtosecond photoexcitation of semiconducting materials leads to the generation of coherent acoustic phonons (CAPs), the behaviours of which are linked to intrinsic and engineered electronic, optical and structural properties. While often studied with pump-probe spectroscopic techniques, the influence of nanoscale structure and morphology on CAP dynamics can be challenging to resolve with these all-optical methods. Here, we used ultrafast electron microscopy (UEM) to resolve variations in CAP dynamics caused by differences in the degree of crystallinity in as-prepared and annealed GaAs lamellae. Following in situ femtosecond photoexcitation, we directly imaged the generation and propagation dynamics of hypersonic CAPs in a mostly amorphous and, following an in situ photothermal anneal, a mostly crystalline lamella. Subtle differences in both the initial hypersonic velocities and the asymptotic relaxation behaviours were resolved via construction of space-time contour plots from phonon wavefronts. Comparison to bulk sound velocities in crystalline and amorphous GaAs reveals the influence of the mixed amorphous-crystalline morphology on CAP dispersion behaviours. Further, an increase in the asymptotic velocity following annealing establishes the sensitivity of quantitative UEM imaging to both structural and compositional variations through differences in bonding and elasticity. Lastly, implications of extending the methods and results reported here to elucidating correlated electronic, optical and structural behaviours in semiconducting materials are discussed.

42 ENGINEERING↗

Functional Relevance of CASP16 Nucleic Acid Predictions as Evaluated by Structure Providers

ABSTRACT Accurate biomolecular structure prediction enables the prediction of mutational effects, the speculation of function based on predicted structural homology, the analysis of ligand binding modes, experimental model building, and many other applications. Such algorithms to predict essential functional and structural features remain out of reach for biomolecular complexes containing nucleic acids. Here, we report a quantitative and qualitative evaluation of nucleic acid structures for the CASP16 blind prediction challenge by 12 of the experimental groups who provided nucleic acid targets. Blind predictions accurately model secondary structure and some aspects of tertiary structure, including reasonable global folds for some complex RNAs; however, predictions often lack accuracy in the regions of highest functional importance. All models have inaccuracies in non‐canonical regions where, for example, the nucleic‐acid backbone bends, deviating from an A‐form helix geometry, or a base forms a non‐standard hydrogen bond (not a Watson‐Crick base pair). These bends and non‐canonical interactions are integral to forming functionally important regions such as RNA enzymatic active sites. Additionally, the modeling of conserved and functional interfaces between nucleic acids and ligands, proteins, or other nucleic acids remains poor. For some targets, the experimental structures may not represent the only structure the biomolecular complex occupies in solution or in its functional life cycle, posing a future challenge for the community.

Biochemistry & Molecular Biology↗

Method for accurately predicting solvation structure

Accurately predicting the molecular structure of solutions is a fundamental scientific challenge. Using quantum mechanical density functional theory (DFT) to make these predictions is hindered by significant variation depending on which DFT functional is used. Here, we present a simple metric that can determine the reliability of a DFT functional for predicting solvation structure. We then show that including a simple interaction term to correct this metric leads to quantitative agreement with experimental measurements of liquid structure. We demonstrate the utility of this method by using it to accurately describe the hydration structure around the Na+ a

basis sets, molecular structure, cluster chemistry↗

Physics vs structure: A systematic benchmark of learning strategies for multi-zone building thermal dynamics

Recent advances in physics-informed and data-driven machine learning promise improved thermal models for advanced building control, yet there is limited quantitative evidence on when added physics structure and architectural complexity are beneficial. Here, this work presents a systematic benchmark of five representative system identification methods for modeling multi-zone building thermal dynamics: linear state-space models, multi-layer perceptrons, neural state-space models, neural ordinary differential equations, and physically-consistent neural networks. The methods are evaluated across multiple data regimes and zone coupling strategies. Using a high-fidelity multi-zone commercial building emulator, we examine short-term and long-term prediction accuracy, computational efficiency, and ease of development. Our results reveal critical trade-offs between prediction performance, model complexity, and physical consistency. We demonstrate that decoupled, nonlinear black-box models consistently outperform coupled physics-constrained architectures in both predictive accuracy and out-of-distribution robustness in majority of the test cases for the building type considered in the study. Our findings quantify the cost of complexity in building thermal modeling and provide concrete, actionable, scenario-based guidelines for selecting model classes for control-oriented applications.

Building thermal modeling↗

Role of orbital selectivity on crystal structures and electronic states in BiMnO 3 and LaMnO 3 perovskites

Correlated oxides, such as BiMnO 3 and LaMnO 3 , show a complex interplay of electronic correlations and crystal structure exhibiting multiple first-order phase transitions, some without a clear order parameter. The quantitative theoretical description of this temperature-dependent electronic-structural interplay in the vicinity of a Mott transition is still a challenge. Here we address this issue by simultaneously considering both structural and electronic degrees of freedom, within a self-consistent density functional theory with embedded dynamical mean field theory. Our results show the existence of novel electronic states characterized by the coexistence of insulating, semimetallic, and metallic orbitals. This state is in agreement with resonant x-ray scattering. Here we also show that electronic entropy plays a decisive role in both electronic and structural phase transitions. By self-consistent determination of both the electronic state and the corresponding crystal structure, we show that the temperature evolution of these phases can be quantitatively explained from first principles, thus demonstrating the predictive power of the theoretical method for both the structural and the electronic properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Designing interagency responses to wicked problems: A viable system model board game

Government agencies struggle to address wicked problems because they are open-ended, highly interdependent issues that cross agency, stakeholder, jurisdictional, and geopolitical boundaries. While both quantitative modelling and qualitative problem structuring methodologies have been used to support interagency decision making in the past, co-designing an effective interagency organization to collaboratively tackle wicked problems is more challenging. Few approaches have been developed to enable such efforts. This paper explains how the viable system model (VSM) was implemented through a board game, which was employed to co-design an interagency meta-organization that would be capable of more effectively collaborating to jointly address a wicked problem: international organized drug crime and its interface with local gangs in Chicago, USA. The board game was developed to make the VSM easier for the participants to learn, given that the cybernetic language and engineering-influenced diagrams in the original literature can be off-putting to leaders and managers. The board game was used as the final stage of a multi-method, systemic approach, which involved boundary critique and problem structuring as well as deployment of the VSM. The research findings indicate that the VSM board game, used as part of a larger mixed-methods systemic intervention, contributes to building trust in the value of systems thinking amongst the participants, and sets up a rich context for collaboration on multi-agency co-design. The game therefore offers significant promise as part of the co-design of interagency responses to wicked problems because it creates an embodied process for stakeholders to learn about the VSM. It also reduces the work involved in this learning. Thus, the game enables an effective appropriation of the VSM language and criteria.

Business & Economics↗

Optimal CO 2 storage management considering safety constraints in multi-stakeholder multi-site GCS projects: A Markov game perspective

Geological carbon storage (GCS) projects could involve a diverse array of stakeholders or players from public, private, and regulatory sectors, each with different objectives and responsibilities. Given the complexity, scale, and long-term nature of GCS operations, determining whether individual stakeholders can independently optimize their interests — or whether collaborative coalition agreements are needed — remains a central question for effective GCS project planning and management. To access large, high-quality storage resources, future GCS deployment may increasingly occur in geologically connected sites, where shared geological features such as pressure space and reservoir pore capacity can lead to competitive behavior among stakeholders. In this work, we propose a paradigm based on Markov games to quantitatively investigate how different coalition structures affect the goals of stakeholders. We frame this multi-stakeholder multi-site problem as a multi-agent reinforcement learning problem with safety constraints. Our approach enables agents to learn optimal strategies while complying with safety regulations. We present an example where multiple operators are injecting CO 2 into their respective project areas in a geologically connected basin. To address the high computational cost of repeated simulations of high fidelity models, a previously developed surrogate model based on the Embed-to-Control (E2C) framework is employed. Our results demonstrate the effectiveness of the proposed framework in addressing optimal management of CO 2 storage when multiple stakeholders with different objectives and goals are involved.

58 GEOSCIENCES↗

Vacuum-ultraviolet absorption cross-sections of functionalized four-carbon species

Absorption cross-sections were measured in the vacuum ultraviolet from 5.17 – 9.92 eV using differential absorption spectroscopy for 33 four-carbon species: n-butane, trans-2-butene, cis-2-butene, butanal, butyric acid, ethyloxirane, trans-2,3-dimethyloxirane, cis-2,3-dimethyloxirane, 2-methyloxetane, 2,2'-bioxirane, vinyl oxirane, 3,4-epoxybutan-2-one, diacetyl, diethyl ether, ethyl vinyl ether, vinyl acetate, acetic anhydride, 1-butanol, 3-buten-1-ol, 1–hydroxy-butan-2-one, 1–hydroxy-butan-3-one, 2,3-epoxybutan-1-ol, 3,4-epoxybutan-1-ol, 2-oxetanemethanol, butanone, methyl vinyl ketone, 4H-1,3-dioxine, allyl formate, 2-oxobutanal, 4-hydroxybutanal, 2-methyloxetan-3-one, cis–but-2-en-1-ol, and trans-2–but-enal. Uncertainties were quantified in all cases by accounting for errors in gas-phase concentration, experimental repeatability, and signal-to-noise ratio as a function of photon energy. With the exception of 2-oxobutanal, which is reported with an uncertainty of 10%, convolving the sources of error using the root-sum-square method led to an upper limit of 5% uncertainty above the detection limit, which is largely attributable to chemical purity. Here, the primary objective of the present work is to provide absolute cross-sections along with quantified uncertainty limits. The majority of the absorption spectra, which reflect electronic transitions such as σ → σ* and n → σ*, are reported for the first time and provide insight into fundamental chemical physics, such as vibrational band structure and Rydberg transitions. The quantitative spectra in the present work facilitates the discovery of chemical intermediates that support improvement in the accuracy of computational models for low-temperature combustion and atmospheric chemistry.

biofuels↗

Quantifying Dissolution Dynamics in Porous Media Using a Spatial Flow Focusing Profile

Abstract The diverse range of patterns in porous media formed by dissolution processes depends on the relative magnitude of flow, transport, and chemical reactions at pore surfaces. However, distinguishing between regimes often relies solely on qualitative, visual comparisons of emergent structures. Here, we propose a quantitative measure capable of identifying different regimes using the concept of the spatial flow focusing profile, which segments the medium into cross sections along the flow direction to calculate the flow focusing index for each section. We employ this measure in numerical simulations of a dissolving porous medium using a pore network model. We obtain a morphological phase diagram of dissolution patterns, which we characterize using the flow focusing profile. In particular, we demonstrate that analyzing the temporal changes in the profile allows one to quantitatively distinguish between wormholing and channeling. The transition between them is shown to be affected by the heterogeneity of the system.

58 GEOSCIENCES↗

Room temperature crystal field splitting of curium resolved by circularly polarized luminescence spectroscopy

Coordination of Cm(III) with a chiral decadentate ligand N,N,N',N'-tetrakis[(6-carboxypyridin-2-yl)methyl]-1,2-diaminocyclohexane (tpadac) generated complexes with strong luminescence allowing for the unprecedented measurement of well-resolved Cm(III) circularly polarized luminescence spectra. Quantitative resolution of the electronic structure of the [Cm(tpadac)][K] complexes was achieved at room temperature, highlighting the strength of the combination of luminescence and circularly polarized luminescence spectroscopies to unravel the fundamental electronic structure of Cm(III). These results are a clear demonstration that these spectroscopies are powerful yet simple tools for the fundamental understanding of electronic structure, which opens the door to future investigations of other Cm(III) complexes in geometries relevant to nuclear applications, and even other 5f-elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward direct spatial and intensity characterization of ultra-high-intensity laser pulses using ponderomotive scattering of free electrons

Spatial distributions of electrons ionized and scattered from ultra-low-pressure gases are proposed and experimentally demonstrated as a method to directly measure the intensity of an ultra-high-intensity laser pulse. Analytic models relating the peak scattered electron energy to the peak laser intensity are derived and compared to paraxial Runge–Kutta simulations highlighting two models suitable for describing electrons scattered from weakly paraxial beams (f#>5) for intensities in the range of 1018−1021 W cm−2. Scattering energies are shown to be dependent on gas species, emphasizing the need for specific gases for given intensity ranges. Direct measurements of the laser intensity at full power of two laser systems are demonstrated, both showing a good agreement between indirect methods of intensity measurement and the proposed method. One experiment exhibited the role of spatial aberrations in the scattered electron distribution, motivating a qualitative study on the effect. We propose the use of convolutional neural networks as a method for extracting quantitative information on the spatial structure of the laser at full power. We believe the presented technique to be a powerful tool that can be immediately implemented in many high-power laser facilities worldwide.

47 OTHER INSTRUMENTATION↗

Design considerations for an ultrahigh-bandwidth Phase Contrast Imaging system applied to fusion grade devices

Abstract The PCI diagnostic is an internal reference interferometer that creates an image of absolutely calibrated electron density fluctuations integrated along the line of sight of the probing light beam. While conventional PCI diagnostics installed on fusion experiments worldwide employ light of wavelength equal to 10.59 μm, the same system using light at 1.55 μm wavelength would extend the spectral response in wave-number and frequency by factors of seven and over one hundred, respectively, thereby potentially providing quantitative measurements of the internal structure of density perturbations induced by either turbulent or radio-frequency waves, simultaneously covering ion to electron gyro-radius scales up to the GHz frequency region. Based on a previously developed 1.55 μm PCI prototype system, constraints to the design for such a diagnostic in fusion grade devices are presented and compared to those faced with the conventional method.

Instruments & Instrumentation↗

Topological band inversion in HgTe(001): Surface and bulk signatures from photoemission

HgTe is a versatile topological material and has enabled the realization of a variety of topological states, including two- and three-dimensional (3D) topological insulators and topological semimetals. Nevertheless, a quantitative understanding of its electronic structure remains challenging, in particular, due to coupling of the Te $5p$-derived valence electrons to Hg $5d$ core states at shallow binding energy. Here, we present a joint experimental and theoretical study of the electronic structure in strained HgTe(001) films in the 3D topological-insulator regime, based on angle-resolved photoelectron spectroscopy and density functional theory. The results establish detailed agreement in terms of: (i) electronic band dispersions and orbital symmetries, (ii) surface and bulk contributions to the electronic structure, and (iii) the importance of Hg $5d$ states in the valence-band formation. Supported by theory, our experiments directly image the paradigmatic band inversion in HgTe, underlying its nontrivial band topology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nanoscale Critical Phenomena in a Complex Fluid Studied by X-ray Photon Correlation Spectroscopy.

The advent of high-speed x-ray photon correlation spectroscopy now allows the study of critical phenomena in fluids to much smaller length scales and over a wider range of temperatures than is possible with dynamic light scattering. We present an x-ray photon correlation spectroscopy study of critical fluctuation dynamics in a complex fluid typical of those used in liquid-liquid extraction (LLE) of ions,dodecane-DMDBTDMA with extracted aqueous Ce(NO 3 ) 3 . We observe good agreement with both staticand dynamic scaling without the need for significant noncritical background corrections. Critical exponents agree with 3D Ising values, and the fluctuation dynamics are described by simple exponential relaxation.The form of the dynamic master curve deviates somewhat from the Kawasaki result, with a more abrupt transition between the critical and noncritical asymptotic behavior. The concepts of critical phenomena thus provide a quantitative framework for understanding the structure and dynamics of LLE systems and a path forward to new LLE processes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effects of Perfluorinated Alkyl Substances (PFAS) on Amphibian Body and Liver Conditions: Is Lipid Metabolism Being Perturbed throughout Metamorphosis?

Per- and polyfluoroalkyl substances (PFAS) may interact with peroxisome proliferator activated receptors (PPARs) and alter lipid homeostasis. Using Xenopus laevis, we investigated the effect of PFAS on (a) lipid homeostasis and whether this correlated to changes in body and hepatic condition; (b) the expression of hepatic genes regulated by PPAR; and (c) the hepatic lipidome. We chronically exposed tadpoles to 0.5 µg/L of either PFOS, PFHxS, PFOA, PFHxA, a binary mixture of PFOS and PFHxS (0.5 µg/L of each), or a control, from NF stage 52 through metamorphic climax. Growth, development, and survival were not affected, but we detected a sex-specific decrease in body condition at NF 66 (6.8%) and in hepatic condition (16.6%) across metamorphic climax for male tadpoles exposed to PFOS. We observed weak evidence for the transient downregulation of apolipoprotein-V (apoa5) at NF 62 in tadpoles exposed to PFHxA. Acyl-CoA oxidase 1 (acox1) was downregulated only in males exposed to PFHxS (Ln(Fold Change) = −0.54). We detected PFAS-specific downregulation of structural glycerophospholipids, while semi-quantitative profiling detected the upregulation in numerous glycerophospholipids, sphingomyelins, and diglycerides. Overall, our findings indicate that PFAS can induce sex-specific effects that change across larval development and metamorphosis. We demonstrate that PFAS alter lipid metabolism at environmentally relevant concentrations through divergent mechanisms that may not be related to PPARs, with an absence of effects on body condition, demonstrating the need for more molecular studies to elucidate mechanisms of PFAS-induced lipid dysregulation in amphibians and in other taxa.

Bushong, Anna (ORCID:0000000249630578)↗

Exploring the Role of Glycans in the Interaction of SARS-CoV-2 RBD and Human Receptor ACE2

COVID-19 is a highly infectious respiratory disease caused by the novel coronavirus SARS-CoV-2. It has become a global pandemic and its frequent mutations may pose new challenges for vaccine design. During viral infection, the Spike RBD of SARS-CoV-2 binds the human host cell receptor ACE2, enabling the virus to enter the host cell. Both the Spike and ACE2 are densely glycosylated, and it is unclear how distinctive glycan types may modulate the interaction of RBD and ACE2. Detailed understanding of these determinants is key for the development of novel therapeutic strategies. To this end, we perform extensive all-atom simulations of the (i) RBD-ACE2 complex without glycans, (ii) RBD-ACE2 with oligomannose MAN9 glycans in ACE2, and (iii) RBD-ACE2 with complex FA2 glycans in ACE2. These simulations identify the key residues at the RBD-ACE2 interface that form contacts with higher probabilities, thus providing a quantitative evaluation that complements recent structural studies. Notably, we find that this RBD-ACE2 contact signature is not altered by the presence of different glycoforms, suggesting that RBD-ACE2 interaction is robust. Applying our simulated results, we illustrate how the recently prevalent N501Y mutation may alter specific interactions with host ACE2 that facilitate the virus-host binding. Furthermore, our simulations reveal how the glycan on Asn90 of ACE2 can play a distinct role in the binding and unbinding of RBD. Finally, an energetics analysis shows that MAN9 glycans on ACE2 decrease RBD-ACE2 affinity, while FA2 glycans lead to enhanced binding of the complex. Together, our results provide a more comprehensive picture of the detailed interplay between virus and human receptor, which is much needed for the discovery of effective treatments that aim at modulating the physical-chemical properties of this virus.

60 APPLIED LIFE SCIENCES↗

Experimental electronic structures of the Fe IV =O bond in S=1 heme vs. nonheme sites: Effect of the porphyrin ligand

High-valent Fe IV =O species are common intermediates in biological and artificial catalysts. Heme and nonheme S=1 Fe IV =O sites have been synthesized and studied for decades but little quantitative experimental comparison of their electronic structures has been available, due to the lack of direct methods focused on the iron. This study allows a rigorous determination of the electronic structure of a nonheme Fe IV =O center and its comparison to an Fe IV =O heme site using 1s2p resonant inelastic X-ray scattering (RIXS) and Fe L-edge X-ray absorption spectroscopy (XAS). Further, variable temperature magnetic circular dichroism (VT-MCD) of the ligand field transitions, combined with nuclear resonance vibrational spectroscopy of the two S=1 Fe IV =O systems show that the equatorial ligand field decreases from a nonheme to a heme Fe IV =O site. Alternatively, RIXS and Fe L-edge XAS combined with MCD show that the Fe dπ orbitals are unperturbed in the Fe IV =O heme relative to the nonheme site because the strong axial Fe-O bond uncouples the Fe dπ orbitals from the porphyrin π-system. As a consequence, the thermodynamics and kinetics of the H-atom abstraction reactions are actually very similar for heme compound II and nonheme Fe IV =O active sites.

bioinorganic chemistry↗