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At least 217 records · Page 12

Atom-diatom scattering dynamics of spinning molecules

We present full quantum mechanical scattering calculations using spinning molecules as target states for nuclear spin selective atom-diatom scattering of reactive D+H{sub 2} and F+H{sub 2} collisions. Molecules can be forced to rotate uni-directionally by chiral trains of short, non-resonant laser pulses, with different nuclear spin isomers rotating in opposite directions. The calculations we present are based on rotational wavepackets that can be created in this manner. As our simulations show, target molecules with opposite sense of rotation are predominantly scattered in opposite directions, opening routes for spatially and quantum state selective scattering of close chemical species. Moreover, two-dimensional state resolved differential cross sections reveal detailed information about the scattering mechanisms, which can be explained to a large degree by a classical vector model for scattering with spinning molecules.

74 ATOMIC AND MOLECULAR PHYSICS↗

Alchemy: A Model-Based Approach for 2D to 3D Autonomous Nuclear System Design

Engineering design of nuclear power plant (NPP) piping and equipment systems frequently bypasses crucial 2D system planning, instead moving straight to 3D modeling. This often leads to designs that exceed building envelope constraints, forcing expensive and time-consuming redesigns. When 2D modeling is employed, it typically involves labor-intensive manual workflows that convert 2D drawings into 3D models, resulting in inefficiencies and errors across design iterations. These workflows further suffer from poor software interoperability and dependence on proprietary software ecosystems, thereby contributing to schedule delays and cost overruns. This paper presents Alchemy, an autonomous framework that transforms 2D system definitions into Industry Foundation Classes (IFC)-compliant 3D building information models (BIMs) for expediting nuclear facility design at the conceptual preliminary phase. Using a model-based approach, the framework treats the 2D system diagram as the central reference model employed to automatically generate all subsequent outputs, ensuring consistency between the system definition and the resulting physical design. A web-based interface enables engineers to define hierarchical system topologies including associated equipment, geometric properties, and connectivity requirements. A two-phase equipment layout optimization algorithm automatically computes collision-free spatial configurations within predefined building envelopes. An artificial intelligence (AI)-assisted pipe routing module then generates orthogonal, collision-free routing paths, allowing the user to select either an A* search-based method or an Ant Colony Optimization (ACO)-based method. All outputs are authored natively in IFC format, relying on open-source technologies and standardized formats in order to ensure extensibility and eliminate proprietary software dependencies. The proposed framework is validated on two representative pressurized-water reactor (PWR)-based case studies, for which it autonomously generates IFC-compliant 3D models in minutes, drastically reducing workflows that typically require hours of manual effort. The generated model demonstrates topologically correct equipment placement, physically plausible spatial relationships, and collision-free pipe routing consistent with known PWR loop configurations. This work represents a foundational step toward digital engineering for nuclear facility preliminary design, with future ongoing development targeting design code compliance and expanded system complexity.

97 - MATHEMATICS AND COMPUTING↗

ProgLIMI: Programmable LInk Metric Identification in Software-Defined Networks

In this paper, we propose the Programmable LInk Metric Identification (ProgLIMI) infrastructure for software-defined networking (SDN) networks. ProgLIMI identifies round-trip link metrics (RTLMs) from accumulated end-to-end metrics of selected measurement paths by leveraging the flexible routing control capability of SDN networks. ProgLIMI mainly solves three sub-problems: (1) monitor placement; (2) linearly independent measurement path construction; and (3) flow rule design. To reduce measurement cost, ProgLIMI tries to minimize the number of required monitors and flow rules. In this paper, we address the three sub-problems for both full and hybrid SDN networks. For full SDN networks, ProgLIMI can achieve full RTLM identification using only one monitor and two flow rules in each SDN switch. In contrast, the RTLM identification in hybrid SDN networks is more complicated due to the routing constraint of hybrid SDN networks. We first prove that the monitor placement problem in hybrid SDN networks is NP-hard. We then formulate the monitor placement and measurement path selection problem in hybrid SDN networks and propose a greedy heuristic algorithm to solve the problem efficiently. Our evaluations on both physical testbed and simulation platform reveal that ProgLIMI can accurately identify the RTLMs (delay and loss rate). Besides, ProgLIMI is also resource efficient, i.e., it only requires two flow rules in each SDN switch and a small number of monitors, and the extra probing traffic load incurred by ProgLIMI is also low.

97 MATHEMATICS AND COMPUTING↗

High-fraction brookite films from amorphous precursors

Structure-specific synthesis processes are of key importance to the growth of polymorphic functional compounds such as TiO 2 , where material properties strongly depend on structure as well as chemistry. The robust growth of the brookite polymorph of TiO 2 , a promising photocatalyst, has been difficult in both powder and thin-film forms due to the disparity of reported synthesis techniques, their highly specific nature, and lack of mechanistic understanding. In this work, we report the growth of high-fraction (~95%) brookite thin films prepared by annealing amorphous titania precursor films deposited by pulsed laser deposition. We characterize the crystallization process, eliminating the previously suggested roles of substrate templating and Na helper ions in driving brookite formation. Instead, we link phase selection directly to film thickness, offering a novel, generalizable route to brookite growth that does not rely on the presence of extraneous elements or particular lattice-matched substrates. In addition to providing a new synthesis route to brookite thin films, our results take a step towards resolving the problem of phase selection in TiO 2 growth, contributing to the further development of this promising functional material.

14 SOLAR ENERGY↗

Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity

In this article, we report on a new route to produce hexane-1,2,5,6-tetrol (tetrol) from cellulose-derived levoglucosanol (lgol). We investigate the reaction intermediates formed over metal and acid catalysts, and propose a reaction network for this process. Lgol is converted to tetrol in up to 90% yield over a bifunctional Pt/SiO 2 –Al 2 O 3 catalyst at 150 °C. High tetrol yields are maintained at lgol concentrations of up to 21 wt% in water. threo- and erythro-lgol first undergo hydrolysis to 3,4-dideoxymannose (DDM) and 3,4-dideoxyglucose (DDG), respectively. This reaction can be carried out selectively over an Amberlyst 70 acid catalyst at a temperature of 100 °C. At a higher temperature of 150 °C with no added catalyst, DDM and DDG undergo aldose–ketose isomerization to 3,4-dideoxyfructose (DDF). DDM is hydrogenated to cis-tetrol over a Pt/SiO 2 catalyst, while DDG is hydrogenated to trans-tetrol. Formation of DDF erases the stereocenter at the C 2 position of lgol, and hydrogenation of DDF produces a nearly 1:1 mixture of cis- and trans-tetrol. Lastly, this catalytic approach to produce tetrol from biomass opens the door to sustainable chemicals derived from tetrol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An embryo of protocells: The capsule of graphene with selective ion channels

In this study, the synthesis of artificial cell is a route for searching the origin of protocell. Here, we create a novel cell model of graphene capsules with selective ion channels, indicating that graphene might be an embryo of protocell membrane. Firstly, we found that the highly oxidized graphene and phospholipid-graphene oxide composite would curl into capsules under a strongly acidic saturated solution of heavy metallic salt solution at low temperature. Secondly, L-amino acids exhibited higher reactivity than D-amino acids on graphene oxides to form peptides, and the formed peptides in the influence of graphene would be transformed into a secondary structure, promoting the formation of left-handed proteins. Lastly, monolayer nanoporous graphene, prepared by unfocused 84 Kr 25+ , has a high selectivity for permeation of the monovalent metal ions ( Rb + > K + > Cs + > Na + > Li + , based on permeation concentration), but does not allow Cl- go through. It is similar to K+ channels, which would cause an influx of K + into capsule of graphene with the increase of pH in the primitive ocean, creating a suitable inner condition for the origin of life. Therefore, we built a model cell of graphene, which would provide a route for reproducing the origin of life.

59 BASIC BIOLOGICAL SCIENCES↗

Integrated Display System for Low Visibility Landing and Surface Operations

This report summarizes the software products and system architectures developed by Lockheed Martin in support of the Low Visibility Landing and Surface Operations (LVLASO) program at NASA Langley Research Center. It presents an overview of the technical aspects, capabilities, and system integration issues associated with an integrated display system (IDS) that collects, processes and presents information to an aircraft flight crew during all phases of landing, roll-out, turn-off, inbound taxi, outbound taxi and takeoff. Communications hardware, drivers, and software provide continuous real-time data at varying rates and from many different sources to the display programs for presentation on a head-down display (HDD) and/or a head-up display (HUD). An electronic moving map of the airport surface is implemented on the HDD which includes the taxi route assigned by air traffic control, a text messaging system, and surface traffic and runway status information. Typical HUD symbology for navigation and control of the aircraft is augmented to provide aircraft deceleration guidance after touchdown to a pilot selected exit and taxi guidance along the route assigned by ATC. HUD displays include scene-linked symbolic runways, runway exits and taxiways that are conformal with the actual locations on the airport surface. Display formats, system architectures, and the various IDS programs are discussed.

Beskenis, Sharon Otero↗

Routing Based on Length of Time of Available Connection

In an embodiment, a method of routing packets at a first node in an ad-hoc network is provided. The method includes receiving, at the first node, a plurality of route-alive messages corresponding to a destination, each of the plurality of route-alive messages including a route time indicating a length of time in which a communicative connection is available between the second node that sent the respective route-alive message and the destination. The method also includes determining an updated route time for each second node. The updated route time corresponds to a length of time in which a communication connection is available between the first node and the destination through the respective second node. A second node is selected for sending a packet to based on the updated route time for each of the second nodes, wherein a node having a longer updated route time is given higher priority for selection.

Anandappan, Thanga↗

A Comparative Study of Ethanol Upgrading to Butadiene Over Rare Earth Elements Incorporated in Dealuminated Beta Zeolites

Copper and rare earth element-containing dealuminated Beta zeolites (CuREE/deAlBeta) are promising catalysts for the conversion of ethanol to C 3+ olefins en route to sustainable aviation fuel. Product selectivities over CuREE/deAlBeta depend on the identity of the REE. Here, in this study, a suite of La/deAlBeta catalysts of varied La loading are prepared, and their reactivities, selectivities, and apparent C-C coupling kinetics in the cascade reaction between ethanol and acetaldehyde are reported. Ex situ and in situ titrations to quantify Lewis acidic La sites quantify distinct numbers of sites, suggesting a distribution of site types. Across a series of REE/deAlBeta catalysts (REE = Y, La, Lu, Yb, Gd), the selectivity to secondary products correlates with the pyridine heats of adsorption at REE Lewis acid sites. The turnover frequency (per Lewis acid site) for C–C coupling was similar across the series of REE/deAlBeta catalysts. Y/deAlBeta and La/deAlBeta, which have the most disparate secondary product selectivities, had similar kinetics for C–C coupling. These findings demonstrate the complexity of quantifying active sites in REE/deAlBeta zeolites, and the sensitivity of the selectivity, but not the reactivity for C–C coupling, to the identity of the REE atom in REE/deAlBeta zeolites.

alcohol upgrading↗

Selective Chemical Looping Combustion of Terminal Alkynes in Mixtures with Alkenes

The selective combustion of terminal alkynes in mixtures with alkenes is demonstrated during anaerobic reduction half-cycles on bulk bismuth oxide (Bi 2 O 3 ) as an approach to remove alkynes, which act as inhibitors in olefin polymerization. Bi 2 O 3 combusts phenylacetylene in styrene, 3-methylphenylacetylene in 3-methylstyrene, propyne in propylene, 1-hexyne in 1-hexene, and 1-octyne in 1-octene, with alkyne combustion selectivities exceeding 96%. Near unity reaction orders for hydrocarbon consumption during reduction half-cycles are consistent with combustion pathways initiated by rate-determining initial C–H activation, which drive selective alkyne combustion through intrinsic differences in the first-order rate constants for alkyne and alkene combustion rather than preferential adsorption of alkynes on Bi 2 O 3 surfaces. Computational assessments of initial C–H activation pathways for alkynes and alkenes on (010) α-Bi 2 O 3 surfaces using density functional theory illustrate that heterolytic transition states which form proton-carbanion pairs on Bi–O sites kinetically favor the activation of alkynes rather than alkenes due to differences in C–H bond acidity, and the barrier for heterolytic C–H activation is dictated in part by the sum of the molecular deprotonation energy and the energy to bind an R – carbanion to a Bi site in its transition-state geometry. Finally, these heterolytic reactivity channels during selective chemical looping combustion present novel routes for purifying olefin gas streams containing alkyne impurities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design and Evaluation of a Dynamic Programming Flight Routing Algorithm Using the Convective Weather Avoidance Model

The optimization of traffic flows in congested airspace with varying convective weather is a challenging problem. One approach is to generate shortest routes between origins and destinations while meeting airspace capacity constraint in the presence of uncertainties, such as weather and airspace demand. This study focuses on development of an optimal flight path search algorithm that optimizes national airspace system throughput and efficiency in the presence of uncertainties. The algorithm is based on dynamic programming and utilizes the predicted probability that an aircraft will deviate around convective weather. It is shown that the running time of the algorithm increases linearly with the total number of links between all stages. The optimal routes minimize a combination of fuel cost and expected cost of route deviation due to convective weather. They are considered as alternatives to the set of coded departure routes which are predefined by FAA to reroute pre-departure flights around weather or air traffic constraints. A formula, which calculates predicted probability of deviation from a given flight path, is also derived. The predicted probability of deviation is calculated for all path candidates. Routes with the best probability are selected as optimal. The predicted probability of deviation serves as a computable measure of reliability in pre-departure rerouting. The algorithm can also be extended to automatically adjust its design parameters to satisfy the desired level of reliability.

Ng, Hok K.↗

Strategies for Choosing Descent Flight-Path Angles for Small Jets

Three candidate strategies for choosing the descent flight path angle (FPA) for small jets are proposed, analyzed, and compared for fuel efficiency under arrival metering conditions. The strategies vary in operational complexity from a universally fixed FPA, or FPA function that varies with descent speed for improved fuel efficiency, to the minimum-fuel FPA computed for each flight based on winds, route, and speed profile. Methodologies for selecting the parameter for the first two strategies are described. The differences in fuel burn are analyzed over a year s worth of arrival traffic and atmospheric conditions recorded for the Dallas/Fort Worth (DFW) Airport during 2011. The results show that the universally fixed FPA strategy (same FPA for all flights, all year) burns on average 26 lbs more fuel per flight as compared to the minimum-fuel solution. This FPA is adapted to the arrival gate (direction of entry to the terminal) and various timespans (season, month and day) to improve fuel efficiency. Compared to a typical FPA of approximately 3 degrees the adapted FPAs vary significantly, up to 1.3 from one arrival gate to another or up to 1.4 from one day to another. Adapting the universally fixed FPA strategy to the arrival gate or to each day reduces the extra fuel burn relative to the minimum-fuel solution by 27% and 34%, respectively. The adaptations to gate and time combined shows up to 57% reduction of the extra fuel burn. The second strategy, an FPA function, contributes a 17% reduction in the 26 lbs of extra fuel burn over the universally fixed FPA strategy. Compared to the corresponding adaptations of the universally fixed FPA, adaptations of the FPA function reduce the extra fuel burn anywhere from 15-23% depending on the extent of adaptation. The combined effect of the FPA function strategy with both directional and temporal adaptation recovers 67% of the extra fuel relative to the minimum-fuel solution.

Wu, Minghong Gilbert↗

Optimization of Material Recycling During the Decommissioning Process of Nuclear Power Plants - 16123

The German Government decided in 2011 to phase out nuclear power. Therefore, in the near future there will be several nuclear power plants queued up, in parallel, for dismantling. In nuclear decommissioning there is no standardized procedure available, so that a high level of optimization potential can be assumed. We present the results of a preliminary study, in which the optimization potential of metal recycling during the dismantling process should be estimated. The project can be roughly divided into four sections: - Determination of the metal inventory of an exemplarily selected plant; - Analysis of the recycling routes of scrap metal fractions and assessment of the potential for optimization of each process step during the dismantling; - Conduction of activation calculations to uncover the potential of interim storage allowing for radioactive decay; - In collaboration with the Institute of Process Metallurgy and Metal Recycling at the RWTH Aachen, appropriate process steps and process chains of an optimized metal recycling for each of the resulting scrap metal fractions are identified. The paper and the presentation summarize the status and the results of the project implementation and will address for the optimization potentials for decommissioning projects. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Tuning Anion Composition and Mobility to Balance Ionic Conductivity and Cation Selectivity in Solid Polymer Electrolytes

Solid polymer electrolytes (SPEs) offer a promising route toward safe and high-performance electrochemical energy storage, yet a fundamental challenge in SPEs involves improving ionic conductivity while maintaining selective cation transport. The hurdle exists because ion transport is typically coupled closely to polymer segmental dynamics. Herein, a glassy single-ion-conducting polymer, poly[lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] (PLiMTFSI), in which the anions were tethered to the polymer, was blended with a flexible polymer, poly(oligo-oxyethylene methyl ether methacrylate) (POEM), and a series of small-molecule lithium salts, in which the anions were untethered [lithium bis(trifluoromethane­sulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoromethanesulfonate (LiTf), or lithium perchlorate (LiClO 4 )]. The impact of salt anion volume and tethered-to-untethered anion ratio on the ion conduction behavior and thermal properties of blend electrolytes was investigated. In some cases, conductivity could be enhanced through this ternary blend approach. For example, a POEM-based polymer blend containing a bulky salt anion (TFSI⁻) and an equimolar mixture of PLiMTFSI and LiTFSI exhibited a Li + conductivity (4.8×10 -4 S/cm) an order of magnitude higher than that of a comparable POEM / LiTFSI system (6.3×10 -5 S/cm) at 100 °C. This enhancement was attributed to a more than ninefold increase in lithium transference number (0.66 in the ternary blend vs. 0.07 in POEM / LiTFSI). Overall, this study highlights the potential for tuning anion composition and mobility to achieve relatively high ionic conductivities and maintain selective cation transport in SPEs, offering a pathway to enable batteries that tolerate elevated temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bacteriochlorin syntheses - Status, problems, and exploration

Bacteriochlorins – Nature’s near-infrared (NIR) chromophores – are distinguished by an intense ([Formula: see text] ∼;10 5 M[Formula: see text]cm[Formula: see text] long-wavelength absorption band in the ∼;700–1000 nm. The development of routes to prepare synthetic, tailorable bacteriochlorins holds promise for multiple disciplines where NIR-light-promoted photoactivity is of interest. A de novo route to bacteriochlorins equipped with a stabilizing gem-dimethyl group in each pyrroline ring was discovered in 2003. Continued development in this arena over 20 years has led to additional routes as well as methods to install substituents at selected positions about the perimeter of the macrocycle. The present paper reports studies that highlight substantial limitations of existing synthetic routes, including stymied access to multi-bacteriochlorin arrays and the inability to install (in a rational way) distinct groups at opposite sides of the macrocycle. The origins of the limitations are traced to particular stages of the chemistry ranging from derivatizing pyrroles, creating pyrrolines, constructing and elaborating dihydrodipyrrins, coupling dihydrodipyrrins, and forming macrocycles. Through exploration of a dozen aspects of bacteriochlorin syntheses, 60 new compounds (and nine known compounds via improved syntheses) have been prepared and characterized; the data include 20 single-crystal X-ray diffraction analyses. The research taken together points to areas of focus to fulfill the promise of this fascinating class of compounds.

Chemistry↗

Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO 2 reduction

Electrochemical reduction of CO 2 is a promising route for sustainable production of fuels. A grand challenge is developing low-cost and efficient electrocatalysts that can enable rapid conversion with high product selectivity. Here we design a series of nickel phthalocyanine molecules supported on carbon nanotubes as molecularly dispersed electrocatalysts (MDEs), achieving CO 2 reduction performances that are superior to aggregated molecular catalysts in terms of stability, activity and selectivity. The optimized MDE with methoxy group functionalization solves the stability issue of the original nickel phthalocyanine catalyst and catalyses the conversion of CO 2 to CO with >99.5% selectivity at high current densities of up to -300 mA cm -2 in a gas diffusion electrode device with stable operation at -150 mA cm -2 for 40 h. The well-defined active sites of MDEs also facilitate the in-depth mechanistic understandings from in situ/operando X-ray absorption spectroscopy and theoretical calculations on structural factors that affect electrocatalytic performance.

42 ENGINEERING↗

Electronically Coupled 2D Polymer/MoS 2 Heterostructures

Emergent quantum phenomena in electronically coupled two-dimensional heterostructures are central to next-generation optical, electronic, and quantum information applications. Tailoring electronic band gaps in coupled heterostructures would permit control of such phenomena and is the subject of significant research interest. Two-dimensional polymers (2DPs) offer a compelling route to tailored band structures through the selection of molecular constituents. However, despite the promise of synthetic flexibility and electronic design, fabrication of 2DPs that form electronically coupled 2D heterostructures remains an outstanding challenge. Here, we report the rational design and optimized synthesis of electronically coupled semiconducting 2DP/2D transition metal dichalcogenide van der Waals heterostructures, demonstrate direct exfoliation of the highly crystalline and oriented 2DP films down to a few nanometers, and present the first thickness-dependent study of 2DP/MoS 2 heterostructures. In this work, control over the 2DP layers reveals enhancement of the 2DP photoluminescence by two orders of magnitude in ultrathin sheets and an unexpected thickness-dependent modulation of the ultrafast excited state dynamics in the 2DP/MoS 2 heterostructure. These results provide fundamental insight into the electronic structure of 2DPs and present a route to tune emergent quantum phenomena in 2DP hybrid van der Waals heterostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective Formation of Acetic Acid and Methanol by Direct Methane Oxidation Using Rhodium Single-Atom Catalysts

Atomically dispersed catalysts such as single-atom catalysts have been shown to be effective in selectively oxidizing methane, promising a direct synthetic route to value-added oxygenates such as acetic acid or methanol. However, an important challenge of this approach has been that the loading of active sites by single-atom catalysts is low, leading to a low overall yield of the products. We report an approach that can address this issue. It utilizes a metal–organic framework built with porphyrin as the linker, which provides high concentrations of binding sites to support atomically dispersed rhodium. It is shown that up to 5 wt% rhodium loading can be achieved with excellent dispersity. When used for acetic acid synthesis by methane oxidation, a new benchmark performance of 23.62 mmol·gcat –1 ·h –1 was measured. Furthermore, the catalyst exhibits a unique sensitivity to light, producing acetic acid (under illumination, up to 66.4% selectivity) or methanol (in the dark, up to 65.0% selectivity) under otherwise identical reaction conditions.

36 MATERIALS SCIENCE↗