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At least 91 records · Page 5

From calibration to parameter learning: Harnessing the scaling effects of big data in geoscientific modeling

Abstract The behaviors and skills of models in many geosciences (e.g., hydrology and ecosystem sciences) strongly depend on spatially-varying parameters that need calibration. A well-calibrated model can reasonably propagate information from observations to unobserved variables via model physics, but traditional calibration is highly inefficient and results in non-unique solutions. Here we propose a novel differentiable parameter learning (dPL) framework that efficiently learns a global mapping between inputs (and optionally responses) and parameters. Crucially, dPL exhibits beneficial scaling curves not previously demonstrated to geoscientists: as training data increases, dPL achieves better performance, more physical coherence, and better generalizability (across space and uncalibrated variables), all with orders-of-magnitude lower computational cost. We demonstrate examples that learned from soil moisture and streamflow, where dPL drastically outperformed existing evolutionary and regionalization methods, or required only ~12.5% of the training data to achieve similar performance. The generic scheme promotes the integration of deep learning and process-based models, without mandating reimplementation.

54 ENVIRONMENTAL SCIENCES↗

The structural basis for regulation of the glutathione transporter Ycf1 by regulatory domain phosphorylation

Yeast Cadmium Factor 1 (Ycf1) sequesters heavy metals and glutathione into the vacuole to counter cell stress. Ycf1 belongs to the ATP binding cassette C-subfamily (ABCC) of transporters, many of which are regulated by phosphorylation on intrinsically-disordered domains. The regulatory mechanism of phosphorylation is still poorly understood. Here, we report two cryo-EM structures of Ycf1 at 3.4 Å and 4.0 Å resolution in inward-facing open conformations that capture previously unobserved ordered states of the intrinsically disordered regulatory domain (R-domain). R-domain phosphorylation is clearly evident and induces a topology promoting electrostatic and hydrophobic interactions with Nucleotide Binding Domain 1 (NBD1) and the Lasso motif. These interactions stay constant between the structures and are related by rigid body movements of the NBD1/R-domain complex. Biochemical data further show R-domain phosphorylation reorganizes the Ycf1 architecture and is required for maximal ATPase activity. Together, we provide insights into how R-domains control ABCC transporter activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Global energy spectrum of the general oceanic circulation

Abstract Advent of satellite altimetry brought into focus the pervasiveness of mesoscale eddies $${{{{{{{\bf{{{{{{{{\mathcal{O}}}}}}}}}}}}}}}}({100})$$ O ( 100 ) km in size, which are the ocean’s analogue of weather systems and are often regarded as the spectral peak of kinetic energy (KE). Yet, understanding of the ocean’s spatial scales has been derived mostly from Fourier analysis in small "representative” regions that cannot capture the vast dynamic range at planetary scales. Here, we use a coarse-graining method to analyze scales much larger than what had been possible before. Spectra spanning over three decades of length-scales reveal the Antarctic Circumpolar Current as the spectral peak of the global extra-tropical circulation, at ≈ 10 4 km, and a previously unobserved power-law scaling over scales larger than 10 3 km. A smaller spectral peak exists at ≈ 300 km associated with mesoscales, which, due to their wider spread in wavenumber space, account for more than 50% of resolved surface KE globally. Seasonal cycles of length-scales exhibit a characteristic lag-time of ≈ 40 days per octave of length-scales such that in both hemispheres, KE at 10 2 km peaks in spring while KE at 10 3 km peaks in late summer. These results provide a new window for understanding the multiscale oceanic circulation within Earth’s climate system, including the largest planetary scales.

54 ENVIRONMENTAL SCIENCES↗

Characterization of paramagnetic states in an organometallic nickel hydrogen evolution electrocatalyst

Abstract Significant progress has been made in the bioinorganic modeling of the paramagnetic states believed to be involved in the hydrogen redox chemistry catalyzed by [NiFe] hydrogenase. However, the characterization and isolation of intermediates involved in mononuclear Ni electrocatalysts which are reported to operate through a Ni I/III cycle have largely remained elusive. Herein, we report a Ni II complex (NCHS2)Ni(OTf)2, where NCHS2 is 3,7-dithia-1(2,6)-pyridina-5(1,3)-benzenacyclooctaphane, that is an efficient electrocatalyst for the hydrogen evolution reaction (HER) with turnover frequencies of ~3,000 s −1 and a overpotential of 670 mV in the presence of trifluoroacetic acid. This electrocatalyst follows a hitherto unobserved HER mechanism involving C-H activation, which manifests as an inverse kinetic isotope effect for the overall hydrogen evolution reaction, and Ni I /Ni III intermediates, which have been characterized by EPR spectroscopy. We further validate the possibility of the involvement of Ni III intermediates by the independent synthesis and characterization of organometallic Ni III complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy

Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kβ main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kβ main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solving complex nanostructures with ptychographic atomic electron tomography

Abstract Transmission electron microscopy (TEM) is essential for determining atomic scale structures in structural biology and materials science. In structural biology, three-dimensional structures of proteins are routinely determined from thousands of identical particles using phase-contrast TEM. In materials science, three-dimensional atomic structures of complex nanomaterials have been determined using atomic electron tomography (AET). However, neither of these methods can determine the three-dimensional atomic structure of heterogeneous nanomaterials containing light elements. Here, we perform ptychographic electron tomography from 34.5 million diffraction patterns to reconstruct an atomic resolution tilt series of a double wall-carbon nanotube (DW-CNT) encapsulating a complex ZrTe sandwich structure. Class averaging the resulting tilt series images and subpixel localization of the atomic peaks reveals a Zr 11 Te 50 structure containing a previously unobserved ZrTe 2 phase in the core. The experimental realization of atomic resolution ptychographic electron tomography will allow for the structural determination of a wide range of beam-sensitive nanomaterials containing light elements.

36 MATERIALS SCIENCE↗

Signatures of polarized chiral spin disproportionation in rare earth nickelates

In rare earth nickelates (RENiO 3 ), electron-lattice coupling drives a concurrent metal-to-insulator and bond disproportionation phase transition whose microscopic origin has long been the subject of active debate. Of several proposed mechanisms, here we test the hypothesis that pairs of self-doped ligand holes spatially condense to provide local spin moments that are antiferromagnetically coupled to Ni spins. These singlet-like states provide a basis for long-range bond and spiral spin order. Using magnetic resonant X-ray scattering on NdNiO 3 thin films, we observe the chiral nature of the spin disproportionated state, with spin spirals propagating along the crystallographic (101) ortho direction. These spin spirals are found to preferentially couple to X-ray helicity, establishing the presence of a hitherto-unobserved macroscopic chirality. The presence of this chiral magnetic configuration suggests a potential multiferroic coupling between the noncollinear magnetic arrangement and improper ferroelectric behavior as observed in prior studies on NdNiO 3 (101) ortho films and RENiO 3 single crystals. Experimentally constrained theoretical double-cluster calculations confirm the presence of an energetically stable spin-disproportionated state with Zhang-Rice singlet-like combinations of Ni and ligand moments

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ten-valley excitonic complexes in charge-tunable monolayer WSe 2

Excitons dominate the optical response of two-dimensional (2D) semiconductors. Strong interactions produce peculiar excitonic complexes, which provide a testing ground for exciton and quantum many-body theories. Here, we report a hitherto unobserved many-body exciton that emerges upon filling both the K and Q valleys of WSe 2 . We optically probe the exciton landscape using charge-tunable devices with unusually thin dielectrics that facilitate doping up to several 10 13 cm −2 . We observe the emergence of the thermodynamically stable complex when 10 valleys are electrostatically filled. We gain insight into its physics using magneto-optical measurements. Our results are well-described by a model where the number of distinguishable Fermi seas interacting with the photoexcited electron-hole pair defines the complex’s behavior. In addition to expanding the repertoire of excitons in 2D semiconductors, this complex could probe the limit of exciton models and answer open questions about screened Coulomb interactions in 2D semiconductors.

M exciton↗

Directional ballistic transport in the two-dimensional metal PdCoO2

Abstract In an idealized infinite crystal, the material properties are constrained by the symmetries of the unit cell. The point-group symmetry is broken by the sample shape of any finite crystal, but this is commonly unobservable in macroscopic metals. To sense the shape-induced symmetry lowering in such metals, long-lived bulk states originating from an anisotropic Fermi surface are needed. Here we show how a strongly facetted Fermi surface and the long quasiparticle mean free path present in microstructures of PdCoO 2 yield an in-plane resistivity anisotropy that is forbidden by symmetry on an infinite hexagonal lattice. We fabricate bar-shaped transport devices narrower than the mean free path from single crystals using focused ion beam milling, such that the ballistic charge carriers at low temperatures frequently collide with both of the side walls that define the channel. Two symmetry-forbidden transport signatures appear: the in-plane resistivity anisotropy exceeds a factor of 2, and a transverse voltage appears in zero magnetic field. Using ballistic Monte Carlo simulations and a numerical solution of the Boltzmann equation, we identify the orientation of the narrow channel as the source of symmetry breaking.

36 MATERIALS SCIENCE↗

Dark states of electrons in a quantum system with two pairs of sublattices

A quantum state of matter that is forbidden to interact with photons and is therefore undetectable by spectroscopic means is called a dark state. This basic concept can be applied to condensed matter where it suggests that a whole band of quantum states could be undetectable across a full Brillouin zone. Here we report the discovery of such condensed-matter dark states in palladium diselenide as a model system that has two pairs of sublattices in the primitive cell. By using angle-resolved photoemission spectroscopy, we find valence bands that are practically unobservable over the whole Brillouin zone at any photon energy, polarization and scattering plane. Our model shows that two pairs of sublattices located at half-translation positions and related by multiple glide-mirror symmetries make their relative quantum phases polarized into only four kinds, three of which become dark due to double destructive interference. This mechanism is generic to other systems with two pairs of sublattices, and we show how the phenomena observed in cuprates, lead halide perovskites and density wave systems can be resolved by the mechanism of dark states. Our results suggest that the sublattice degree of freedom, which has been overlooked so far, should be considered in the study of correlated phenomena and optoelectronic characteristics.

electronic properties and materials↗

High-resolution tunnelling spectroscopy of fractional quantum Hall states

Strong interactions between electrons in two-dimensional systems in the presence of a high magnetic field give rise to fractional quantum Hall states that host quasiparticles with a fractional charge and fractional exchange statistics. Here, in this work, we demonstrate high-resolution scanning tunnelling microscopy and spectroscopy of fractional quantum Hall states in ultra-clean Bernal-stacked bilayer graphene devices. Spectroscopy measurements show sharp excitations that have been predicted to emerge when electrons fractionalize into bound states of quasiparticles. We found energy gaps for candidate non-abelian fractional states that are larger by a factor of five than those in other related systems, for example, semiconductor heterostructures, and this suggests that bilayer graphene is an ideal platform for manipulating these quasiparticles and for creating topological quantum bits. We also found previously unobserved fractional states in our very clean graphene samples.

quantum Hall↗

Revised monthly energy generation estimates for 1,500 hydroelectric power plants in the United States

Abstract The U.S. Energy Information Administration (EIA) conducts a regular survey (form EIA-923) to collect annual and monthly net generation for more than ten thousand U.S. power plants. Approximately 90% of the ~1,500 hydroelectric plants included in this data release are surveyed at annual resolution only and thus lack actual observations of monthly generation. For each of these plants, EIA imputes monthly generation values using the combined monthly generating pattern of other hydropower plants within the corresponding census division. The imputation method neglects local hydrology and reservoir operations, rendering the monthly data unsuitable for various research applications. Here we present an alternative approach to disaggregate each unobserved plant’s reported annual generation using proxies of monthly generation—namely historical monthly reservoir releases and average river discharge rates recorded downstream of each dam. Evaluation of the new dataset demonstrates substantial and robust improvement over the current imputation method, particularly if reservoir release data are available. The new dataset—named RectifHyd—provides an alternative to EIA-923 for U.S. scale, plant-level, monthly hydropower net generation (2001–2020). RectifHyd may be used to support power system studies or analyze within-year hydropower generation behavior at various spatial scales.

13 HYDRO ENERGY↗

A deep generative model enables automated structure elucidation of novel psychoactive substances

Over the past decade, the illicit drug market has been reshaped by the proliferation of clandestinely produced designer drugs. These agents, referred to as new psychoactive substances (NPSs), are designed to mimic the physiological actions of better-known drugs of abuse while skirting drug control laws. The public health burden of NPS abuse obliges toxicological, police and customs laboratories to screen for them in law enforcement seizures and biological samples. However, the identification of emerging NPSs is challenging due to the chemical diversity of these substances and the fleeting nature of their appearance on the illicit market. Here, in this study, we present DarkNPS, a deep learning-enabled approach to automatically elucidate the structures of unidentified designer drugs using only mass spectrometric data. Our method employs a deep generative model to learn a statistical probability distribution over unobserved structures, which we term the structural prior. We show that the structural prior allows DarkNPS to elucidate the exact chemical structure of an unidentified NPS with an accuracy of 51% and a top-10 accuracy of 86%. Our generative approach has the potential to enable de novo structure elucidation for other types of small molecules that are routinely analysed by mass spectrometry.

Cheminformatics↗

Identifiability and predictability of integer- and fractional-order epidemiological models using physics-informed neural networks

Here we analyze a plurality of epidemiological models through the lens of physics-informed neural networks (PINNs) that enable us to identify time-dependent parameters and data-driven fractional differential operators. In particular, we consider several variations of the classical susceptible-infectious-removed (SIR) model by introducing more compartments and fractional-order and time-delay models. We report the results for the spread of COVID-19 in New York City, Rhode Island and Michigan states and Italy, by simultaneously inferring the unknown parameters and the unobserved dynamics. For integer-order and time-delay models, we fit the available data by identifying time-dependent parameters, which are represented by neural networks. In contrast, for fractional differential models, we fit the data by determining different time-dependent derivative orders for each compartment, which we represent by neural networks. We investigate the structural and practical identifiability of these unknown functions for different datasets, and quantify the uncertainty associated with neural networks and with control measures in forecasting the pandemic.

60 APPLIED LIFE SCIENCES↗

Risk-Oriented PMU Placement Approach in Electric Power Systems

The objective of traditional PMU placement approaches is to use the minimal number of PMUs to cover system complete observability. Very few consider the probability and the consequence severity of observability loss. For example, following line trip, grid topology changes, which may results in observability loss and overloaded lines. As long as the overloaded lines are still observable, then we can take action in time to correct the system; and the consequence of the observability loss is not severe, although some parts of the system is not observable. Otherwise, if the overloaded lines become unobservable, then we lose the situation awareness of the system and the consequence of the observability loss is severe. To address the above points in PMU placement, this paper proposes a risk-oriented PMU placement approach. The proposed approach uses two indices, namely the probability of observability loss and its corresponding consequence of severity to design the optimal PMU placement strategy. We show that our proposed approach is able to capture the critical events while the traditional approaches fail to do so. Extensive simulation results carried out on the IEEE 39-bus and 118-bus systems demonstrate its effectiveness.

observability, risk of observability loss, PMUs pl↗

Extended-magnetohydrodynamics in under-dense plasmas

Extended-magnetohydrodynamics (MHD) transports magnetic flux and electron energy in high-energy-density experiments, but individual transport effects remain unobserved experimentally. Two factors are responsible in defining the transport: electron temperature and electron current. Here, each electron energy transport term has a direct analog in magnetic flux transport. To measure the thermally driven transport of magnetic flux and electron energy, a simple experimental configuration is explored computationally using a laser-heated pre-magnetized under-dense plasma. Changes to the laser heating profile precipitate clear diagnostic signatures from the Nernst, cross-gradient-Nernst, anisotropic conduction, and Righi-Leduc heat-flow. With a wide operating parameter range, this configuration can be used in both small and large scale facilities to benchmark MHD and kinetic transport in collisional/semi-collisional, local/non-local, and magnetized/unmagnetized regimes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Characterizing magnetized plasmas with dynamic mode decomposition

Accurate and efficient plasma models are essential to understand and control experimental devices. Existing magnetohydrodynamic or kinetic models are nonlinear and computationally intensive and can be difficult to interpret, while often only approximating the true dynamics. In this work, data-driven techniques recently developed in the field of fluid dynamics are leveraged to develop interpretable reduced-order models of plasmas that strike a balance between accuracy and efficiency. In particular, dynamic mode decomposition (DMD) is used to extract spatio-temporal magnetic coherent structures from the experimental and simulation datasets of the helicity injected torus with steady inductive (HIT-SI) experiment. Three-dimensional magnetic surface probes from the HIT-SI experiment are analyzed, along with companion simulations with synthetic internal magnetic probes. A number of leading variants of the DMD algorithm are compared, including the sparsity-promoting and optimized DMD. Optimized DMD results in the highest overall prediction accuracy, while sparsity-promoting DMD yields physically interpretable models that avoid overfitting. These DMD algorithms uncover several coherent magnetic modes that provide new physical insights into the inner plasma structure. These modes were subsequently used to discover a previously unobserved three-dimensional structure in the simulation, rotating at the second injector harmonic. Finally, using data from probes at experimentally accessible locations, DMD identifies a resistive kink mode, a ubiquitous instability seen in magnetized plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Ensemble flow reconstruction in the atmospheric boundary layer from spatially limited measurements through latent diffusion models

Due to costs and practical constraints, field campaigns in the atmospheric boundary layer typically only measure a fraction of the atmospheric volume of interest. Machine learning techniques have previously successfully reconstructed unobserved regions of flow in canonical fluid mechanics problems and two-dimensional geophysical flows, but these techniques have not yet been demonstrated in the three-dimensional atmospheric boundary layer. Here, we conduct a numerical analogue of a field campaign with spatially limited measurements using large-eddy simulation. We pose flow reconstruction as an inpainting problem, and reconstruct realistic samples of turbulent, three-dimensional flow with the use of a latent diffusion model. The diffusion model generates physically plausible turbulent structures on larger spatial scales, even when input observations cover less than 1% of the volume. Through a combination of qualitative visualization and quantitative assessment, we demonstrate that the diffusion model generates meaningfully diverse samples when conditioned on just one observation. These samples successfully serve as initial conditions for a large-eddy simulation code. We find that diffusion models show promise and potential for other applications for other turbulent flow reconstruction problems.

17 WIND ENERGY↗