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At least 937 records · Page 52

Girsanov's transformation based variance reduced Monte Carlo simulation schemes for reliability estimation in nonlinear stochastic dynamics

The study considers the problem of simulation based time variant reliability analysis of nonlinear randomly excited dynamical systems. Attention is focused on importance sampling strategies based on the application of Girsanov's transformation method. Controls which minimize the distance function, as in the first order reliability method (FORM), are shown to minimize a bound on the sampling variance of the estimator for the probability of failure. Two schemes based on the application of calculus of variations for selecting control signals are proposed: the first obtains the control force as the solution of a two-point nonlinear boundary value problem, and, the second explores the application of the Volterra series in characterizing the controls. The relative merits of these schemes, vis-à-vis the method based on ideas from the FORM, are discussed. Illustrative examples, involving archetypal single degree of freedom (dof) nonlinear oscillators, and a multi-degree of freedom nonlinear dynamical system, are presented. The credentials of the proposed procedures are established by comparing the solutions with pertinent results from direct Monte Carlo simulations. - Highlights: • The distance minimizing control forces minimize a bound on the sampling variance. • Establishing Girsanov controls via solution of a two-point boundary value problem. • Girsanov controls via Volterra's series representation for the transfer functions.

97 MATHEMATICS AND COMPUTING↗

Diabatization with Electrostatic Embedding for Studying Photophysics in Organic Molecular Crystals

Highly emissive organic molecular crystals find applications in several areas, such as organic electronics, solar cells, and sensors. Understanding the excited-state mechanisms underlying these applications is essential for optimizing and controlling them effectively. Exciton models coupled with nonadiabatic dynamics, particularly quantum dynamics, provide crucial insights into photochemical and photophysical processes in molecular crystals. Nevertheless, there remains a lack of general tools and automated workflows to facilitate such simulations. In this paper, we present a computational strategy to investigate the photoactivated dynamics of organic molecular crystals, bridging methodologies traditionally used for molecular systems and materials science, with a particular focus on the interplay between local excitations and charge transfer (CT) processes. We have implemented an interface between the fromage and Overdia programs, enabling the construction of vibronic Hamiltonians for molecular crystals within an excited-state ONIOM(QM:QM′) framework, incorporating long-range electrostatics through a RESP-based Ewald summation. Fragment-based diabatization provides a route to quantum dynamics simulations in weak-to-intermediate coupling regimes. The method was applied to the photophysics of dibenzo[g,p]chrysene (DBC) crystals using time-dependent DFT. The fromage/ Overdia interface was employed to compute the couplings of local excitations and CT states for 18 unique DBC dimers in the crystal and to quantify the influence of electrostatic embedding, which was found to be modest (10−20%). Simulations on π-stacked dimers reproduced the small red shift observed experimentally from solution to crystal, attributed to electronic interactions among fixed monomers rather than crystal electrostatics. Quantum dynamics simulations revealed ultrafast population transfer from bright local excitations to CT states. This approach establishes a robust framework linking molecular and solid-state excited-state dynamics, with potential applications for studying excitations, defects, and impurities in molecular crystals.

Crystals↗

The fluorescence quantum yield parameter in Förster resonance energy transfer (FRET)—Meaning, misperception, and molecular design

The fluorescence quantum yield parameter in Förster resonance energy transfer (FRET) processes underpins vital phenomena ranging from light harvesting in photosynthesis to design of sensors for monitoring physiological processes. The criteria for choosing a donor for use in FRET processes include chemical features (solubility, bioconjugatability, synthetic accessibility, and stability) as well as photophysical properties pertaining to absorption (wavelength and molar absorption coefficient) and fluorescence (wavelength and fluorescence quantum yield). The value of the donor fluorescence quantum yield (Φf, or emphatically, Φf(D)) alone has sometimes been thought (erroneously) to place a ceiling on the possible quantum yield of energy transfer (Φtrans). A high value of the donor Φf, while attractive, is not at all essential; indeed, many valuable candidates for use as FRET donors have likely been excluded on the basis of this injudiciously applied filter. Such disregard is unwarranted. In this tutorial overview, the equations for FRET are reviewed along with pertinent core concepts in photophysics. An analogy using simple hydraulics provides a pedagogical tool for the non-aficionado to better understand photochemical kinetics. Ten examples are presented of donor–acceptor systems with donors that exhibit a range of Φf values (0.60, 0.59. 0.21, 0.17, 0.12, 0.118, 0.04, 0.018, 0.007, and 0.003; i.e., 60%–0.3%), yet for each corresponding donor–acceptor pair, the value of Φtrans is at least 0.70 and in some cases nearly 1.00 (i.e., 70%–100%). The systems encompass protein, synthetic inorganic, and synthetic organic architectures. The objectives of this illustrative review are to deepen understanding of FRET and to broaden molecular design considerations by enabling selection from among a far richer set of donors for use in FRET processes.

Lindsey, Jonathan S. (ORCID:0000000248722040)↗

High-Resolution Frequency-Domain Spectroscopic and Modeling Studies of Photosystem I (PSI), PSI Mutants and PSI Supercomplexes

Photosystem I (PSI) is one of the two main pigment–protein complexes where the primary steps of oxygenic photosynthesis take place. This review describes low-temperature frequency-domain experiments (absorption, emission, circular dichroism, resonant and non-resonant hole-burned spectra) and modeling efforts reported for PSI in recent years. In particular, we focus on the spectral hole-burning studies, which are not as common in photosynthesis research as the time-domain spectroscopies. Experimental and modeling data obtained for trimeric cyanobacterial Photosystem I (PSI 3 ), PSI 3 mutants, and PSI 3 –IsiA 18 supercomplexes are analyzed to provide a more comprehensive understanding of their excitonic structure and excitation energy transfer (EET) processes. Detailed information on the excitonic structure of photosynthetic complexes is essential to determine the structure–function relationship. We will focus on the so-called “red antenna states” of cyanobacterial PSI, as these states play an important role in photochemical processes and EET pathways. The high-resolution data and modeling studies presented here provide additional information on the energetics of the lowest energy states and their chlorophyll (Chl) compositions, as well as the EET pathways and how they are altered by mutations. We present evidence that the low-energy traps observed in PSI are excitonically coupled states with significant charge-transfer (CT) character. The analysis presented for various optical spectra of PSI 3 and PSI 3 -IsiA 18 supercomplexes allowed us to make inferences about EET from the IsiA 18 ring to the PSI 3 core and demonstrate that the number of entry points varies between sample preparations studied by different groups. In our most recent samples, there most likely are three entry points for EET from the IsiA 18 ring per the PSI core monomer, with two of these entry points likely being located next to each other. Therefore, there are nine entry points from the IsiA 18 ring to the PSI 3 trimer. We anticipate that the data discussed below will stimulate further research in this area, providing even more insight into the structure-based models of these important cyanobacterial photosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Critical Impact of Graphene Functionalization for Transition Metal Oxide/Graphene Hybrids on Oxygen Reduction Reaction

Transition metal oxides (TMOs) anchored on a carbon nanostructure have been widely pursued for oxygen reduction reaction (ORR) catalysis. The high ORR activity of TMO/graphene has been often attributed to the synergistic nature between TMO and carbon but with little relevant mechanistic study. In this report, the focus is made on how the type of majority oxygen-containing functional group of graphene affects the ORR performance of the resulting TMO/graphene nanocomposites. Our TiO 2 /carboxylated graphene and ZrO 2 /hydroxylated graphene rendered an ORR activity very close to that of Pt/C with an equal mass loading, via a four-electron transfer dominant process unlike other TMO/graphene variants of study. It is revealed that a stable anchoring of nanoparticles (NPs) on the graphene surface, which is essential to prevent the restacking of graphene layers, is established only through a specific type of functional groups on the graphene. In addition, the interplay among TMOs, graphene, and functional groups is found to be deterministic in the activity and electron transfer pathway of ORR, which is supported by density function theory (DFT) calculations. Finally, the calculations indicate that the electron transfer pathway is dependent upon the structure of NPs interfacing with functional groups of the graphene as it affects the preferred sites for oxygen dissociation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solar Irradiation Induced Transformation of Ferrihydrite in the Presence of Aqueous Fe 2+

Ferrihydrite commonly occurs in soils and sediments, especially in acid mine drainage (AMD). Solar irradiation may affect Fe(II)-catalyzed transformation of metastable ferrihydrite to more stable iron oxides on AMD surface. We investigated the Fe(II)-catalyzed transformation process and mechanism of ferrihydrite under light irradiation. In nitrogen atmosphere, Fe 2+ aq could be oxidized to goethite and lepidocrocite by hydroxyl radical (OH • ), superoxide radical (O 2 •– ) and hole (h vb + ) generated from ferrihydrite under ultraviolet (UV) irradiation (300–400 nm) at pH 6.0, and O 2 •– and h vb + were mainly responsible for Fe 2+ aq oxidation. In addition, the ligand-to-metal charge-transfer (LMCT) process between Fe(II) and ferrihydrite could be promoted by UV irradiation. Goethite proportion increased with increasing Fe 2+ aq concentration. Both visible (vis) and solar irradiation could also lead to the oxidation of Fe 2+ aq to goethite and lepidocrocite, and the proportion of lepidocrocite increased with increasing light intensity. Fe 2+ aq was photochemically oxidized to schwertmannite at pH 3.0 and 4.5, and the oxidation rate was higher than that under dark conditions in air. The photochemical oxidation rate of Fe 2+ aq decreased in the presence of humic acid. This study facilitates a better understanding of the formation and transformation of iron oxides in natural environments and ancient Earth.

54 ENVIRONMENTAL SCIENCES↗

Excitation-Dependent High-Lying Excitonic Exchange via Interlayer Energy Transfer from Lower - to - Higher Bandgap 2D Material

High light absorption (~15%) and strong photoluminescence (PL) emission in monolayer (1L) transition metal dichalcogenides (TMDs) make them ideal candidates for optoelectronic device applications. Competing interlayer charge transfer (CT) and energy transfer (ET) processes control the photocarrier relaxation pathways in TMD heterostructures (HSs). In TMDs, long-distance ET can survive up to several tens of nm, unlike the CT process. Our experiment shows that an efficient ET occurs from the 1Ls WSe 2 -to-MoS 2 with an interlayer hexagonal boron nitride (hBN), due to the resonant overlapping of the high-lying excitonic states between the two TMDs, resulting in enhanced HS MoS 2 PL emission. This type of unconventional ET from the lower-to-higher optical bandgap material is not typical in the TMD HSs. With increasing temperature, the ET process becomes weaker due to the increased electron–phonon scattering, destroying the enhanced MoS 2 emission. Our work provides new insight into the long-distance ET process and its effect on the photocarrier relaxation pathways.

2D material↗

Color Change Upconversion Mechanism of Y{sub 6}O{sub 5}F{sub 8}: Er{sup 3+}/Yb{sup 3+} Microtubes by Using Time-Resolve Spectra

The mechanism of the upconversion processes in Y{sub 6}O{sub 5}F{sub 8}: 2%Er{sup 3+}/X%Yb{sup 3+} (X = 3, 10, 20) microtubes has been explored. The luminescent properties of the as prepared sample is investigated by utilizing up- /downconversion, decay and time resolve spectra. The results indicate that the red and green emission are clearly competitive depending on the Yb{sup 3+} concentration. High Yb{sup 3+} concentration induces the enhancement of the energy-back-transfer (EBT), process, which leads to the quenching of green emission and enhances the red emission. So it is possible to utilize the temporal evolutions of emission bands to deeply understand the color change UC mechanisms.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Controlling Proton-Coupled Electron Transfer in Bioinspired Artificial Photosynthetic Relays

Bioinspired constructs consisting of benzimi- dazole-phenol moieties bearing N-phenylimines as proton-accepting substituents have been designed to mimic the H-bond network associated with the TyrZ-His190 redox relay in photosystem II. These compounds provide a platform to theoretically and experimentally explore and expand proton-coupled electron transfer (PCET) processes. The models feature H-bonds between the phenol and the nitrogen at the 3-position of the benzimidazole and between the 1H-benzimidazole proton and the imine nitrogen. Protonation of the benzimidazole and the imine can be unambiguously detected by infrared spectroelectrochemistry (IRSEC) upon oxidation of the phenol. DFT calculations and IRSEC results demonstrate that with sufficiently strong electron-donating groups at the para-position of the N-phenylimine group (e.g., -OCH3 substitution), proton transfer to the imine is exergonic upon phenol oxidation, leading to a one-electron, two-proton (E2PT) product with the imidazole acting as a proton relay. When transfer of the second proton is not sufficiently exergonic (e.g., -CN substitution), a one-electron, one-proton transfer (EPT) product is dominant. Thus, the extent of proton translocation along the H-bond network, either ~1.6 Å or ~6.4 Å, can be controlled through imine substitution. Moreover, the H-bond strength between the benzimidazole NH and the imine nitrogen, which is a function of their relative pKa values, and the redox potential of the phenoxyl radical/phenol couple are linearly correlated with the Hammett constants of the substituents. In all cases, a high potential (~1 V vs SCE) is observed for the phenoxyl radical/phenol couple. Designing and tuning redox-coupled proton wires is important for understanding bioenergetics and developing novel artificial photosynthetic systems.

Odella, Emmanuel↗

A stochastic scan strategy for grain structure control in complex geometries using electron beam powder bed fusion

Spatial control of microstructure within a three-dimensional component has been a dream of materials scientists for centuries. However, limitations in traditional manufacturing processes prevent detailed control over the distribution of microstructures in a single part. Here, we demonstrate the ability to control grain structure and crystallographic texture during metal additive manufacturing for arbitrary cross-sections of a practical size, with profound implications for the design and optimization of next-generation products. The key to this advance is a new geometry agnostic scan path algorithm that manipulates the spatial distribution of solidification conditions. Utilizing a fundamental understanding of solidification dynamics and a model of the heat transfer during processing, we have designed this algorithm to manipulate the natural competition between epitaxial dendrite growth and grain nucleation. With this algorithm, we successfully controlled the grain structure of Ni-based superalloy IN718 in the shape of the Mona Lisa.

36 MATERIALS SCIENCE↗

Dry etching of epitaxial InGaAs/InAlAs/InAlGaAs structures for fabrication of photonic integrated circuits

A dry etching process to transfer the pattern of a photonic integrated circuit design for high-speed laser communications is described. The laser stack under consideration is a 3.2-µm-thick InGaAs/InAlAs/InAlGaAs epitaxial structure grown by molecular beam epitaxy. The etching was performed using Cl2-based inductively-coupled-plasma and reactive-ion-etching (ICP-RIE) reactors. Four different recipes are presented in two similar ICP-RIE reactors, with special attention paid to the etched features formed with various hard mask compositions, in-situ passivations, and process temperatures. The results indicate that it is possible to produce high-aspect-ratio features with sub-micron separation on this multilayer structure. Additionally, the results of the etching highlight the tradeoffs involved with the corresponding recipes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sensing the Ocean Biological Carbon Pump from Space: A Review of Capabilities, Concepts, Research Gaps and Future Developments

The element carbon plays a central role in climate and life on Earth. It is capable of moving among the geosphere, cryosphere, atmosphere, biosphere and hydrosphere. This flow of carbon is referred to as the Earth's carbon cycle. It is also intimately linked to the cycling of other elements and compounds. The ocean plays a fundamental role in Earth's carbon cycle, helping to regulate atmospheric CO2 concentration. The ocean biological carbon pump (OBCP), defined as a set of processes that transfer organic carbon from the surface to the deep ocean, is at the heart of the ocean carbon cycle. Monitoring the OBCP is critical to understanding how the Earth's carbon cycle is changing. At present, satellite remote sensing is the only tool available for viewing the entire surface ocean at high temporal and spatial scales. In this paper, we review methods for monitoring the OBCP with a focus on satellites. We begin by providing an overview of the OBCP, defining and describing the pools of carbon in the ocean, and the processes controlling fluxes of carbon between the pools, from the surface to the deep ocean, and among ocean, land and atmosphere. We then examine how field measurements, from ship and autonomous platforms, complement satellite observations, provide validation points for satellite products and lead to a more complete view of the OBCP than would be possible from satellite observations alone. A thorough analysis is then provided on methods used for monitoring the OBCP from satellite platforms, covering current capabilities, concepts and gaps, and the requirement for uncertainties in satellite products. We finish by discussing the potential for producing a satellite-based carbon budget for the oceans, the advantages of integrating satellite-based observations with ecosystem models and field measurements, and future opportunities in space, all with a view towards bringing satellite observations into the limelight of ocean carbon research.

Robert J. W. Brewin↗

Geometry-Induced Spatial Variation of Microstructure Evolution During Selective Electron Beam Melting of Rene-N5

High gamma prime (γ') nickel-based alloys produced by selective electron beam melting are of interest to the turbine industry which requires control of microstructure in relation to loading conditions within complex component geometry. Welding literature predicts cracking and microstructure evolution as a function of alloy composition and process parameters in this class of alloys. In addition, Additive manufacturing causes variations in the above conditions due to the interaction of geometry on processing and heat transfer. The influence of geometry on processing conditions was explored for alloy Rene N5 by characterizing the solidification grain microstructure and solid-state precipitation. A Semi-Analytical Heat Transfer Model was employed to explain the resulting variation in solidification grain morphology that occurred due to the part geometry. Finally, the as-built precipitation structure was found to vary as a function of build height and had no correlation to the solidification grain structure or the layer geometry.

36 MATERIALS SCIENCE↗

Extended-Charge-Transfer Excitons in Crystalline Supramolecular Photocatalytic Scaffolds

Coupling among chromophores in molecular assemblies is responsible for phenomena such as resonant energy transfer and intermolecular charge transfer. These processes are central to the fields of organic photovoltaics and photocatalysis, where it is necessary to funnel energy or charge to specific regions within the system. As such, a fundamental understanding of these transport processes is essential for developing new materials for photovoltaic and photocatalytic applications. Recently, photocatalytic systems based on photosensitizing perylene monomimide (PMI) chromophore amphiphiles were found to show variation in hydrogen gas (H 2 ) production as a function of nanostructure crystallinity. The 2D crystalline systems form in aqueous electrolyte solution, which provides a high dielectric environment where the Coulomb potential between charges is mitigated. This results in relatively weakly bound excitons that are ideal for reducing protons. Furthermore, in order to understand how variations in crystalline structure affect H 2 generation, two representative PMI systems are investigated theoretically using a modified Holstein Hamiltonian. The Hamiltonian includes both molecular Frenkel excitations (FE) and charge-transfer excitations (CTE) coupled nonadiabatically to local intramolecular vibrations. Signatures of FE/CTE mixing and the extent of electron/hole separation are identified in the optical absorption spectrum and are found to correlate strongly to the observed H 2 production rates. The absorption spectral signatures are found to sensitively depend on the relative phase between the electron and hole transfer integrals, as well as the diabatic energy difference between the Frenkel and CT exciton bands. Our analysis provides design rules for artificial photosynthetic systems based on organic chromophore arrays.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Numerical and experimental analysis of mechanically induced failure in electric vehicle battery modules

Mitigating thermal runaway and cell-to-cell propagation is essential for improving the safety of electric and hybrid vehicles. Enhancing digital twin capabilities to predict battery mechanical abuse is particularly critical for automotive and aerospace applications, where crashworthiness is a key concern. Understanding failure conditions and propagation in battery modules during mechanical abuse is complex due to interactions between structural deformation, heat transfer, electrochemical processes, exothermic reactions and mechanical fracture. While prior studies have focused on modeling cell-level behavior, extending these models to module or pack level is necessary for a system level understating of electric vehicle safety. This study develops coupled large deformation finite element models that simultaneously solve for electrochemistry, material failure, internal short circuit and thermal runaway propagation. The models account for mechanical and thermal interactions between lithium-ion cells and other battery components while the contact interfaces are evolving with time. Model-predicted voltage, temperature and force responses are compared with experimental data for validation. The results demonstrate that the approach captures key failure mechanisms, including thermal propagation through heat transfer, electrical propagation from short circuits in parallel-connected cells, and mechanical propagation via penetration and crack formation. These findings show that computational models are valuable tools for understanding battery module failure and providing insight that can reduce the need for extensive experimental testing.

25 ENERGY STORAGE↗

Manufacturing a 9-Meter Thermoplastic Composite Wind Turbine Blade: Preprint

Currently, wind turbine blades are manufactured from a combination of glass and/or carbon fiber composite materials with a thermoset resin such as epoxy, which requires energy-intensive and expensive heating processes to cure. Newly developed in-situ polymerizing thermoplastic resin systems for composite wind turbine blades polymerize at room temperature, eliminating the heating process and significantly reducing the blade manufacturing cycle time and embodied energy, which in turn reduces costs. Thermoplastic materials can also be thermally welded, eliminating the need for adhesive bonds between blade components and increasing the overall strength and reliability of the blades. As well, thermoplastic materials enable end-of-life blade recycling by reheating and decomposing the materials, which is a limitation of existing blade technology. This paper presents a manufacturing demonstration for a 9-m-long thermoplastic composite wind turbine blade. This blade was constructed in the Composites Manufacturing Education and Technology facility at the National Wind Technology Center at the National Renewable Energy Laboratory (NREL) using a vacuum-assisted resin transfer molding process. Johns Manville fiberglass and an Arkema thermoplastic resin called Elium were used. Additional materials included Armacell-recycled polyethylene terephthalate foam from Creative Foam and low-cost carbon- fiber pultruded spar caps (manufactured in collaboration with NREL, Oak Ridge National Laboratory, Huntsman, Strongwell, and Chomarat). This paper highlights the development of the thermoplastic resin formulations, including an additive designed to control the peak exothermic temperatures. Infusion and cure times of less than 3 hours are also demonstrated, highlighting the efficiency and energy savings associated with manufacturing thermoplastic composite blades.

17 WIND ENERGY↗

A life cycle and product type based estimator for quantifying the carbon stored in wood products

Background: Timber harvesting and industrial wood processing laterally transfer the carbon stored in forest sectors to wood products creating a wood products carbon pool. The carbon stored in wood products is allocated to end-use wood products (e.g., paper, furniture), landfill, and charcoal. Wood products can store substantial amounts of carbon and contribute to the mitigation of greenhouse effects. Therefore, accurate accounts for the size of wood products carbon pools for different regions are essential to estimating the land-atmosphere carbon exchange by using the bottom-up approach of carbon stock change. Results: To quantify the carbon stored in wood products, we developed a state-of-the-art estimator (Wood Products Carbon Storage Estimator, WPsCS Estimator) that includes the wood products disposal, recycling, and waste wood decomposition processes. The wood products carbon pool in this estimator has three subpools: (1) end-use wood products, (2) landfill, and (3) charcoal carbon. In addition, it has a user-friendly interface, which can be used to easily parameterize and calibrate an estimation. To evaluate its performance, we applied this estimator to account for the carbon stored in wood products made from the timber harvested in Maine, USA, and the carbon storage of wood products consumed in the United States. Conclusion: The WPsCS Estimator can efficiently and easily quantify the carbon stored in harvested wood products for a given region over a specific period, which was demonstrated with two illustrative examples. In addition, WPsCS Estimator has a user-friendly interface, and all parameters can be easily modified.

54 ENVIRONMENTAL SCIENCES↗

Charge Transfer in 2D Halide Perovskites and 2D/3D Heterostructures

Halide perovskites have emerged as a versatile class of materials, with applications spanning photovoltaics, light-emitting diodes, transistors, and photodetectors. The introduction of semiconducting ligands to form two-dimensional (2D) perovskites on the surface of three-dimensional (3D) perovskites in perovskite solar cells has been shown to enhance the performance and stability. To improve the interface properties between the 3D perovskite layer and charge carrier transport layers, understanding the charge transfer (CT) process in 2D perovskites is crucial. In this Perspective, we address common terminological inaccuracies in energy level descriptions, delineate methods for energy alignment characterization, and present practical instances of CT in 2D perovskite-incorporated solar cells. Furthermore, we emphasize the significance of precise terminology, appropriate measurement techniques, and rational design of 2D ligands to harness the full potential of 2D perovskites in optoelectronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗