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At least 631 records · Page 35

Rapid vertical exchange at fronts in the Northern Gulf of Mexico

Over the Texas-Louisiana Shelf in the Northern Gulf of Mexico, the eutrophic, fresh Mississippi/Atchafalaya river plume isolates saltier waters below, supporting the formation of bottom hypoxia in summer. The plume also generates strong density fronts, features of the circulation that are known pathways for the exchange of water between the ocean surface and the deep. Using high-resolution ocean observations and numerical simulations, we demonstrate how the summer land-sea breeze generates rapid vertical exchange at the plume fronts. We show that the interaction between the land-sea breeze and the fronts leads to convergence/divergence in the surface mixed layer, which further facilitates a slantwise circulation that subducts surface water along isopycnals into the interior and upwells bottom waters to the surface. This process causes significant vertical displacements of water parcels and creates a ventilation pathway for the bottom water in the northern Gulf. The ventilation of bottom water can bypass the stratification barrier associated with the Mississippi/Atchafalaya river plume and might impact the dynamics of the region’s dead zone.

54 ENVIRONMENTAL SCIENCES↗

Large-scale physically accurate modelling of real proton exchange membrane fuel cell with deep learning

Proton exchange membrane fuel cells, consuming hydrogen and oxygen to generate clean electricity and water, suffer acute liquid water challenges. Accurate liquid water modelling is inherently challenging due to the multi-phase, multi-component, reactive dynamics within multi-scale, multi-layered porous media. In addition, currently inadequate imaging and modelling capabilities are limiting simulations to small areas (<1 mm 2 ) or simplified architectures. Herein, an advancement in water modelling is achieved using X-ray micro-computed tomography, deep learned super-resolution, multi-label segmentation, and direct multi-phase simulation. The resulting image is the most resolved domain (16 mm 2 with 700 nm voxel resolution) and the largest direct multi-phase flow simulation of a fuel cell. This generalisable approach unveils multi-scale water clustering and transport mechanisms over large dry and flooded areas in the gas diffusion layer and flow fields, paving the way for next generation proton exchange membrane fuel cells with optimised structures and wettabilities.

25 ENERGY STORAGE↗

Tomography of entangling two-qubit logic operations in exchange-coupled donor electron spin qubits

Scalable quantum processors require high-fidelity universal quantum logic operations in a manufacturable physical platform. Donors in silicon provide atomic size, excellent quantum coherence and compatibility with standard semiconductor processing, but no entanglement between donor-bound electron spins has been demonstrated to date. Here we present the experimental demonstration and tomography of universal one- and two-qubit gates in a system of two weakly exchange-coupled electrons, bound to single phosphorus donors introduced in silicon by ion implantation. We observe that the exchange interaction has no effect on the qubit coherence. We quantify the fidelity of the quantum operations using gate set tomography (GST), and we use the universal gate set to create entangled Bell states of the electrons spins, with fidelity 91.3 ± 3.0%, and concurrence 0.87 ± 0.05. These results form the necessary basis for scaling up donor-based quantum computers.

42 ENGINEERING↗

MHC-II dynamics are maintained in HLA-DR allotypes to ensure catalyzed peptide exchange

Presentation of antigenic peptides by major histocompatibility complex class II (MHC-II) proteins determines T helper cell reactivity. The MHC-II genetic locus displays a large degree of allelic polymorphism influencing the peptide repertoire presented by the resulting MHC-II protein allotypes. During antigen processing, the human leukocyte antigen (HLA) molecule HLA-DM (DM) encounters these distinct allotypes and catalyzes exchange of the placeholder peptide CLIP by exploiting dynamic features of MHC-II. Here, we investigate 12 highly abundant CLIP-bound HLA-DRB1 allotypes and correlate dynamics to catalysis by DM. Despite large differences in thermodynamic stability, peptide exchange rates fall into a target range that maintains DM responsiveness. A DM-susceptible conformation is conserved in MHC-II molecules, and allosteric coupling between polymorphic sites affects dynamic states that influence DM catalysis. As exemplified for rheumatoid arthritis, we postulate that intrinsic dynamic features of peptide–MHC-II complexes contribute to the association of individual MHC-II allotypes with autoimmune disease.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The NEON Daily Isotopic Composition of Environmental Exchanges Dataset

The National Ecological Observatory Network (NEON) provides open-access measurements of stable isotope ratios in atmospheric water vapor (δ 2 H, δ 18 O) and carbon dioxide (δ 13 C) at different tower heights, as well as aggregated biweekly precipitation samples (δ 2 H, δ 18 O) across the United States. These measurements were used to create the NEON Daily Isotopic Composition of Environmental Exchanges (NEON-DICEE) dataset estimating precipitation (P; δ 2 H, δ 18 O), evapotranspiration (ET; δ 2 H, δ 18 O), and net ecosystem exchange (NEE; δ 13 C) isotope ratios. Statistically downscaled precipitation datasets were generated to be consistent with the estimated covariance between isotope ratios and precipitation amounts at daily time scales. Isotope ratios in ET and NEE fluxes were estimated using a mixing-model approach with calibrated NEON tower measurements. NEON-DICEE is publicly available on HydroShare and can be reproduced or modified to fit user specific applications or include additional NEON data records as they become available. The NEON-DICEE dataset can facilitate understanding of terrestrial ecosystem processes through their incorporation into environmental investigations that require daily δ 2 H, δ 18 O, and δ 13 C flux data.

54 ENVIRONMENTAL SCIENCES↗

Ultrafast optical observation of spin-pumping induced dynamic exchange coupling in ferromagnetic semiconductor/metal bilayer

Abstract Spin angular momentum transfer in magnetic bilayers offers the possibility of ultrafast and low-loss operation for next-generation spintronic devices. We report the field- and temperature- dependent measurements on the magnetization precessions in Co 2 FeAl/(Ga,Mn)As by time-resolved magneto-optical Kerr effect. Analysis of the effective Gilbert damping and phase shift indicates a clear signature of an enhanced dynamic exchange coupling between the two ferromagnetic (FM) layers due to the reinforced spin pumping at resonance. The temperature dependence of the dynamic exchange-coupling reveals a primary contribution from the ferromagnetism in (Ga,Mn)As.

30 DIRECT ENERGY CONVERSION↗

N-type molecular doping of a semicrystalline conjugated polymer through cation exchange

Control of electrical doping is indispensable in any semiconductor device, and both efficient hole and electron doping are required for many devices. In organic semiconductors, however, electron doping has been essentially more problematic compared to hole doping because in general organic semiconductors have low electron affinities and require dopants with low ionization potentials that are often air-sensitive. Here, we adapt an efficient molecular doping method, so-called ion-exchange doping, to dope electrons in a polymeric semiconductor. We initially reduce the polymeric semiconductor using one electron transfer from molecular dopants, and then the ionized dopants in the resulting air-unstable films are replaced with secondary ions via cation exchange. Improved ambient stability and crystallinity of the doped polymeric semiconductors are achieved when a specific bulky molecular cation was chosen as the secondary ion, compared to conventional methods. The presented strategy can overcome the trade-off relationship between reducing capability and ambient stability in molecular dopants, and a wider selection of dopant ions will help to realize ambient-stable electron conductors.

36 MATERIALS SCIENCE↗

Crosslinked metallo-polyelectrolytes with enhanced flexibility and dimensional stability for anion-exchange membranes

High-performing anion-exchange membranes (AEMs) have attracted tremendous interest for applications in emerging energy storage and conversion devices. In this work, we present a strategy for the synthesis of crosslinked metallo-polyelectrolytes as mechanically flexible, dimensionally stable and ionically conductive AEMs. The water uptake and swelling ratio are suppressed remarkably by introducing a crosslinked polymeric network. The as-prepared membranes also exhibit excellent thermal stability. The phase-separated morphology allows rapid ion-transport with low water uptake at various temperatures. Specifically, a conductivity of 53.3 mS cm -1 at 80 °C was achieved with an ion exchange capacity of 1.07 mmol g -1 and a low swelling ratio of 13%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modulation of H + /H - exchange in iridium-hydride 2-hydroxypyridine complexes by remote Lewis acids

In this study, a series of iridium hydride complexes featuring dihydrogen bonding are presented and shown to undergo rapid H + /H - exchange (1240 s -1 at 25 °C). We demonstrate that the H + /H - exchange rate can be modified by post-synthetic modification at a remote site using BH 3 , Zn(C 6 F 5 ) 2 , and [Me 3 O][BF 4 ]. This route provides a complementary strategy to traditional methods that rely on pre-metalation modifications to a metal's primary sphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adsorption and exchange reactions of iodine molecules at the alumina surface: modelling alumina-iodine reaction mechanisms

Harnessing aluminum oxidation energy requires navigating the particle's passivation shell composed of alumina. The shell is a barrier to aluminum oxidation but can also exothermically react with halogenated species and therefore contribute to the overall energy generated during aluminum particle combustion. Fluorination reactions with alumina have been studied because fluorine is abundant in binder formulations that commonly surround aluminum particles in an energetic mixture. However, iodine has emerged as an alternative halogenated-based binder or oxidizer because iodine gas provides ancillary benefits such as chemical neutralization of biological agents or sterilization of contaminated environments. Furthermore, this study used density functional theory (DFT) calculations to evaluate potential reaction pathways for aluminum–iodine combustion. Relative to fluorinated fragments such as HF and F – , the adsorption energies associated with HI and I– are nearly triple the exchange reaction energy available from fluorination reactions with alumina (–189 and –278 kJ mol –1 for HI and I – , respectively). However, exchange reactions between iodinated species and the alumina surface are energetically unfavorable. These results explain that through adsorption, alumina surface exothermic reactions with iodine are more energetic than with fluorine fragments. Experiments performed with differential scanning calorimetry (DSC) confirm the higher magnitude of energy generated for iodination compared with fluorination reactions with alumina. Additionally, strong adsorption energies can promote synthesis of new shell chemistries. Adsorption in solution will promote alumina dissolution and iodine precipitation reactions to produce hydroxyl complexes and iodinated species synthesized on the surface of the particle, thereby replacing alumina with alternative passivation shell chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revisiting trends in the exchange current for hydrogen evolution

Nørskov and collaborators proposed a simple kinetic model to explain the volcano relation for the hydrogen evolution reaction on transition metal surfaces such that j 0 = k 0 f(ΔG H ) where j 0 is the exchange current density, f(ΔG H ) is a function of the hydrogen adsorption free energy ΔG H as computed from density functional theory, and k 0 is a universal rate constant. Herein, focusing on the hydrogen evolution reaction in acidic medium, we revisit the original experimental data and find that the fidelity of this kinetic model can be significantly improved by invoking metal-dependence on k 0 such that the logarithm of k 0 linearly depends on the absolute value of ΔG H . Here, we further confirm this relationship using additional experimental data points obtained from a critical review of the available literature. Our analyses show that the new model decreases the discrepancy between calculated and experimental exchange current density values by up to four orders of magnitude. Furthermore, we show the model can be further improved using machine learning and statistical inference methods that integrate additional material properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Silver salt enabled H/D exchange at the β-position of thiophene rings: synthesis of fully deuterated thiophene derivatives

Here, we disclose a silver catalyzed H/D exchange reaction, which can introduce the deuterium atom at the β position of thiophene rings without the assistance of any coordinating groups. The advantages of this reaction include operation in open air, usage of D 2 O as the deuterium source, good tolerance to a range of functional groups and obtaining high atom% deuterium incorporation. In addition, this H/D exchange reaction is employed for direct deuteration of a thiophene based monomer, which is usually prepared by multistep synthesis from expensive deuterated starting materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance and durability of anion exchange membrane water electrolyzers using down-selected polymer electrolytes

Over the last decade, several stable anion exchange polymer electrolytes have been developed for electrochemical devices. Herein, we investigate how chemical structure and physical properties of polymer electrolytes affect performance and durability of anion exchange membrane water electrolyzers (AEMWEs). We select polymer electrolytes with high alkaline stability and consider their polymer properties including conductivity, mechanical/chemical stability, and material interactions to interpret the performance and durability of AEMWEs. Here, the AEMWE with a poly(phenylene) membrane and a poly(fluorene) ionomeric binder exhibited the best performance among those tested in this study; the AEMWE showed ~1 A cm –2 at 2 V under 1 wt% K 2 CO 3 -fed conditions. The voltage degradation rate was 270–550 μV h –1 for several hundred operating hours at a constant current density of 750 mA cm –2 and a differential pressure of 100 pounds per square inch gauge. Based on these results, we discuss research needs of polymer electrolytes for practical AEMWEs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NiFeCo-based catalysts in high current zero-gap anion exchange membrane water electrolyzers

Understanding degradation mechanisms in pure water anion exchange membrane water electrolyzers is essential for developing durable and precious metal-free hydrogen production systems, yet electronic, chemical, and transport-driven pathways often occur simultaneously at the anode. To separate these effects, we establish a morphology invariant Ni/Fe/Co thin film model catalyst platform using physical vapor deposition and systematically compare composition-dependent behavior under both pure water and 0.1 M KOH feeds. Devices were operated under industrially relevant current density conditions, galvanostatically at 1 A cm −2 for 24 hours; metal dissolution, ionomer oxidation, and resistance growth were quantified using inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy. Under pure-water operation, Ni-rich films showed voltage increases that correlated with rising total cell resistance (ΔV ≈ 243 mV, ΔR ≈ 0.17 Ω cm 2 ). Co-rich films maintained near constant voltages with minimal resistance change (ΔV < 10 mV, ΔR ≈ 0.03 Ω cm 2 ) but induced pronounced ionomer oxidation observed by XPS. In 0.1 M KOH, ionomer oxidation is suppressed, and impedance growth is minimized (<0.08 Ω cm 2 ) across all compositions, consistent with reduced transport limitations and improved ionic conduction relative to pure-water feeds. These results demonstrate how a controlled thin film model platform can isolate composition electrolyte relationships and provide mechanistic design principles for stable pure water anion exchange membrane electrolyzers.

Milenia Rojas Mendoza, B. [Stanford Univ., CA (Uni↗

A path to scaling helium-3 spin-exchange optical pumping

Polarized 3 He has contributed to breakthroughs in particle physics, neutron scattering, and lung imaging, mostly by optical pumping of liter quantities in valved cells or in sealed cells pumped in situ. Only metastability exchange optical pumping currently meets the demand for delivering large quantities of highly polarized 3 He to external volumes. Our development program is under way to achieve medium to large-scale spin-exchange optical pumping of 3 He. Thin-walled aluminosilicate cells placed in contact with thermal reservoirs inside a pressure vessel were optically pumped with kilowatt-scale lasers spectrally narrowed to match pressure-broadened absorption linewidths. We report here the key elements of this program and significant milestones: multi-liter volume valved cells that provide long longitudinal lifetimes that reached polarization as high as 85% inside a thermally stable and pressurized environment.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Ion temperature and rotation fluctuation measurements with ultra-fast charge exchange recombination spectroscopy (UF-CHERS) in the DIII-D tokamak

An upgraded detector and several optimizations have significantly improved the Ultra-Fast Charge Exchange Recombination Spectroscopy (UF-CHERS) diagnostic sensitivity to ion temperature and parallel velocity fluctuations at turbulence relevant spatio-temporal scales. Normalized broadband ion temperature and parallel velocity fluctuations down to x̃x∼1% (x = Ti, v∥) and up to ∼450 kHz have been measured in a variety of plasmas. The multi-field nature of the CHERS technique also allows measurements of the cross-phase angles of the fluctuating fields. UF-CHERS is optimized to observe emissions from the electron exchange reaction between intrinsic C6+ and hydrogenic neutral beam injected particles near 529 nm. UF-CHERS consists of two chords separated by ∼1 cm radially, less than the turbulence correlation length in DIII-D plasmas, which enables correlated measurements to suppress incoherent electronic and photon noise. The optical components of the spectrometer include a volume-phase-holographic grating with >90% transmission between 528 and 530 nm and f/2 200-mm lenses, selected to maximize the optical efficiency and photon flux. Diffracted light from each chord is collected in eight spectral bins, each with a bandwidth of ∼0.25 nm, and detected and amplified by chilled avalanche photodiodes and custom high-gain, wide bandwidth low-noise preamplifiers to achieve the optimal signal-to-noise ratio. The resulting signals are digitized at 1 MHz, 103–104× faster than the conventional CHERS diagnostics. Spatial coverage is achieved by repositioning a motorized fiber tray between plasmas. UF-CHERS measurements will advance the understanding of turbulent ion transport and contribute to the validation of transport models and simulations.

Truong, D. D. (ORCID:0000000285732539)↗