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At least 469 records · Page 26

Physical drivers facilitating a toxigenic cyanobacterial bloom in a major Great Lakes tributary

The Maumee River is the primary source for nutrients fueling seasonal Microcystis -dominated blooms in western Lake Erie's open waters though such blooms in the river are infrequent. The river also serves as source water for multiple public water systems and a large food services facility in northwest Ohio. On 20 September 2017, an unprecedented bloom was reported in the Maumee River estuary within the Toledo metropolitan area, which triggered a recreational water advisory. Here we (1) explore physical drivers likely contributing to the bloom's occurrence, and (2) describe the toxin concentration and bacterioplankton taxonomic composition. A historical analysis using 10-years of seasonal river discharge, water level, and local wind data identified two instances when high-retention conditions occurred over ≥ 10 d in the Maumee River estuary: in 2016 and during the 2017 bloom. Observation by remote sensing imagery supported the advection of cyanobacterial cells into the estuary from the lake during 2017 and the lack of an estuary bloom in 2016 due to a weak cyanobacterial bloom in the lake. A rapid-response survey during the 2017 bloom determined levels of the cyanotoxins, specifically microcystins, in excess of recreational contact limits at sites within the lower 20 km of the river while amplicon sequencing found these sites were dominated by Microcystis . These results highlight the need to broaden our understanding of physical drivers of cyanobacterial blooms within the interface between riverine and lacustrine systems, particularly as such blooms are expected to become more prominent in response to a changing climate.

54 ENVIRONMENTAL SCIENCES↗

Ultrafast Carrier Self-Trapping Driven by Strong Exciton–Phonon Coupling in 2D MA 3 Bi 2 I 6 Cl 3 Perovskite

Two-dimensional (2D) hybrid bismuth halide perovskites have emerged as promising lead-free materials for optoelectronic applications due to their solution processability and tunable structures. Here, in this study, we investigate 2D layered hybrid perovskite MA 3 Bi 2 I 6 Cl 3 using temperature-dependent photoluminescence (PL) and femtosecond transient absorption spectroscopy. Our results reveal strong coupling between excitons and phonons, evidenced by giant Huang–Rhys factors, coherent phonon oscillations, and ultrafast carrier self-trapping into small-polaron and self-trapped exciton (STE) states. These processes appear as time-dependent ground-state bleach and photoinduced absorption features, highlighting the influence of the lattice in carrier dynamics. Wavelength- and time-resolved measurements reveal that PL emission is dominated by STEs, while free exciton emission is weak and short-lived. By comparing 2D MA 3 Bi 2 I 6 Cl 3 with 0D MA 3 Bi 2 I 9 , which contains molecularly isolated [BiI 6 ] 3− octahedra and 2D MA 3 Bi 2 Br 9 perovskites, we demonstrate how halide composition and structural dimensionality influence the balance between free exciton populations and carrier localization. These insights uncover the intrinsic kinetic landscape of photoexcited states in MA 3 Bi 2 I 6 Cl 3 . Overall, our study contributes to a mechanistic understanding of exciton–phonon interactions in lead-free 2D perovskites.

Pradeep, Kodimana Ramakrishnan [Northwestern Univ.↗

Amplification of primordial perturbations from the rise or fall of the inflaton

The next generation of cosmic microwave background, gravitational wave, and large scale structure, experiments will provide an unprecedented opportunity to probe the primordial power spectrum on small scales. An exciting possibility for what lurks on small scales is a sharp rise in the primordial power spectrum: this can lead to the formation of primordial black holes, providing a dark matter candidate or the black holes observed by the LIGO-Virgo collaboration. In this study we develop a mechanism for the amplification of the small-scale primordial power spectrum, in the context of single-field inflation with a step-like feature in the inflaton potential. Specifically, we consider both the upward and the downward step in the potential. We also discuss the possibility of the strong coupling between perturbations because the rapid changes of the potential derivatives with the time-dependent field value, caused by the step-like feature, could make the coupling stronger. As a result, we find that the perturbations can remain weakly coupled yet sufficiently enhanced if the step realizes the rapid changes of the potential derivatives in some fraction of an e-fold, Script O(P R 1/2) ≲ ΔN < 1, where P R is the power spectrum of the curvature perturbation at that time. We also discuss the PBH formation rate from the inflaton trapping at the local minimum, which can occur in the potential with an upward step.

79 ASTRONOMY AND ASTROPHYSICS↗

Large Fermi surface expansion through anisotropic mixing of conduction and $\textit{f}$ electrons in the semimetallic Kondo lattice CeBi

Using angle-resolved photoemission spectroscopy (ARPES) and resonant ARPES, we report evidence of strong anisotropic conduction-$\textit{f}$ electron mixing ($\textit{c-f}$ mixing) in CeBi by observing a largely expanded Ce 5$d$ pocket at low temperature, with no change in the Bi-6$\textit{p}$ bands. We note the Fermi surface (FS) expansion is accompanied by a pronounced spectral weight transfer from the local 4$f^0$ peak of Ce (corresponding to Ce 3+ ) to the itinerant conduction bands near the Fermi level. Careful analysis suggests that the observed large FS change (with a volume expansion of the electron pocket up to 40%) can most naturally be explained by a small valence change (~1%) of Ce, which coexists with a very weak Kondo screening. Our work therefore provides evidence for a FS change driven by real charge fluctuations deep in the Kondo limit, which are made possible by the low carrier density. Our results highlight the large tunability of the FS in low carrier density Kondo systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Dark-matter-enhanced probe of relic neutrino clustering

We propose heavy decaying dark matter (DM) as a new probe of the cosmic neutrino background (C⁢𝜈⁢B). Heavy DM, with mass ≳ 10 9 GeV, decaying into neutrinos can be a new source of ultrahigh-energy (UHE) neutrinos. Including this contribution along with the measured astrophysical and predicted cosmogenic neutrino fluxes, we study the scattering of UHE neutrinos with the C⁢𝜈⁢B via standard weak interactions mediated by the 𝑍 boson. We solve the complete neutrino transport equation, taking into account both absorption and reinjection effects, to calculate the expected spectrum of UHE neutrino flux at future neutrino telescopes, such as the IceCube-Gen2 radio. We argue that such observations can be used to probe the C⁢𝜈⁢B properties and, in particular, local C⁢𝜈⁢B clustering. We find that, depending on the absolute neutrino mass and the DM mass and lifetime, a local C⁢𝜈⁢B overdensity ≳ 10 6 can be probed at the IceCube-Gen2 radio within ten years of data taking.

Dark matter↗

Effect of Controlled Artificial Disorder on the Magnetic Properties of EuFe 2 (As 1– x P x ) 2 Ferromagnetic Superconductor

Static (DC) and dynamic (AC, at 14 MHz and 8 GHz) magnetic susceptibilities of single crystals of a ferromagnetic superconductor, EuFe 2 ( As 1 – x P x ) 2 ( x = 0.23), were measured in pristine state and after different doses of 2.5 MeV electron or 3.5 MeV proton irradiation. The superconducting transition temperature, T c ( H ) , shows an extraordinarily large decrease. It starts at T c ( H = 0 ) ≈ 24 K in the pristine sample for both AC and DC measurements, but moves to almost half of that value after moderate irradiation dose. Remarkably, after the irradiation not only T c moves significantly below the FM transition, its values differ drastically for measurements at different frequencies, ≈16 K in AC measurements and ≈12 K in a DC regime. We attribute such a large difference in T c to the appearance of the spontaneous internal magnetic field below the FM transition, so that the superconductivity develops directly into the mixed spontaneous vortex-antivortex state where the onset of diamagnetism is known to be frequency-dependent. We also examined the response to the applied DC magnetic fields and studied the annealing of irradiated samples, which almost completely restores the superconducting transition. Overall, our results suggest that in EuFe 2 ( As 1 – x P x ) 2 superconductivity is affected by local-moment ferromagnetism mostly via the spontaneous internal magnetic fields induced by the FM subsystem. Another mechanism is revealed upon irradiation where magnetic defects created in ordered Eu 2 + lattice act as efficient pairbreakers leading to a significant T c reduction upon irradiation compared to other 122 compounds. On the other hand, the exchange interactions seem to be weakly screened by the superconducting phase leading to a modest increase of T m (less than 1 K) after the irradiation drives T c to below T m . Our results suggest that FM and SC phases coexist microscopically in the same volume.

36 MATERIALS SCIENCE↗

Tailoring the growth and electronic structures of organic molecular thin films

In the rapidly developing electronics industry, it has become increasingly necessary to explore materials that are cheap, flexible and versatile which have led to significant research efforts towards organic molecular thin films. Organic molecules are unique compared to their inorganic atomic counterparts as their properties can be tuned drastically through chemical functionalization, offering versatility, though their extended shape and weak intermolecular interactions bring significant challenges to the control of both the growth and the electronic structures of molecular thin films. Herein, we will review the self-assembly process and how to establish long-range ordered organic molecular thin films. We will also discuss how the electronic structures of thin films are impacted by the molecule’s local electrostatic environment and its interaction with the substrate, within the context of controlling interfacial energy level alignment between organic semiconductors and electrodes in electronic devices.

36 MATERIALS SCIENCE↗

Experimental Demonstration of Dark‐State Metasurface Laser with Controllable Radiative Coupling

Abstract Lasing at the nanoscale using plasmonic nanoparticles offers the prospect of strong field concentration, hence strong light−matter interactions, low lasing thresholds, and ultrafast operation. However plasmonic nanoparticles suffer from high dissipative and radiative losses, the latter being rigidly tied to the shape of the nanoparticles and symmetry of their localized plasmon resonant modes. To overcome this limitation, recent theoretical work proposes using direct lasing into dark surface states to construct lasers that conceptually allow for independent implementation of the lasing state and its coherent radiation output. Here, lasing in dark resonant states of a metasurface laser and controllable coherent outcoupling of radiation with the aid of a tightly coupled, weakly radiative metasurface are demonstrated experimentally. The laser is implemented using a thin, low‐loss dielectric film supporting surface mode‐like dark dielectric bound states and the coupling metasurface is composed of small non‐resonant scatterers that controllably but weakly perturb the dark mode and turn it partially bright. Distinct far‐field signatures that can be observed experimentally for both dark and bright lasing are identified and demonstrated. The scalability of this design, here implemented for lasing in the near‐infrared, enables large‐aperture ultra‐thin coherent light sources with controllable emission from the infrared to the visible.

36 MATERIALS SCIENCE↗

Analyticity and the Unruh effect: a study of local modular flow

The Unruh effect can be formulated as the statement that the Minkowski vacuum in a Rindler wedge has a boost as its modular flow. In recent years, other examples of states with geometrically local modular flow have played important roles in understanding energy and entropy in quantum field theory and quantum gravity. Here I initiate a general study of the settings in which geometric modular flow can arise, showing (i) that any geometric modular flow must be a conformal symmetry of the background spacetime, and (ii) that in a well behaved class of “weakly analytic” states, geometric modular flow must be future-directed. I further argue that if a geometric transformation is conformal but not isometric, then it can only be realized as modular flow in a conformal field theory. Finally, I discuss a few settings in which converse results can be shown — i.e., settings in which a state can be constructed whose modular flow reproduces a given vector field.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A pair of early- and late-forming galaxy cluster samples: A novel way of studying halo assembly bias assisted by a constrained simulation

The halo assembly bias, a phenomenon referring to dependencies of the large-scale bias of a dark matter halo other than its mass, is a fundamental property of the standard cosmological model. First discovered in 2005 from the Millennium Run simulation, it has been proven very difficult to be detected observationally, with only a few convincing claims of detection so far. The main obstacle lies in finding an accurate proxy of the halo formation time. In this study, by utilizing a constrained simulation that can faithfully reproduce the observed structures larger than 2 Mpc in the local universe, for a sample of 634 massive clusters at z ≤ 0.12, we found their counterpart halos in the simulation and used the mass growth history of the matched halos to estimate the formation time of the observed clusters. This allowed us to construct a pair of early- and late-forming clusters, with a similar mass as measured via weak gravitational lensing, and large-scale biases differing at the ≈3σ level, suggestive of the signature of assembly bias, which is further corroborated by the properties of cluster galaxies, including the brightest cluster galaxy and the spatial distribution and number of member galaxies. Our study paves a way to further detect assembly bias based on cluster samples constructed purely on observed quantities.

79 ASTRONOMY AND ASTROPHYSICS↗

Plasmon excitations in chemically heterogeneous nanoarrays

The capability of collective excitations, such as localized surface plasmon resonances, to produce a versatile spectrum of optical phenomena is governed by the interactions within the collective and single-particle responses in the finite system. In many practical instances, plasmonic metallic nanoparticles and arrays are either topologically or chemically heterogeneous, which affects both the constituent transitions and their interactions. Here, the formation of collective excitations in weakly Cu- and Pd-doped Au nanoarrays is described using time-dependent density functional theory. The additional impurity-induced modes in the optical response can be thought to result from intricate interactions between separated excitations or transitions. In this work, we investigate the heterogeneity at the impurity level, the symmetry aspects related to the impurity position, and the influence of the impurity position on the confinement phenomena. The chemically rich and symmetry-dependent quantum mechanical effects are analyzed with transition contribution maps demonstrating the possibility to develop nanostructures with more controlled collective properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Global weak solutions for a nonlocal multispecies Fokker–Planck–Landau system

The global-in-time existence of weak solutions to a spatially homogeneous multispecies Fokker–Planck–Landau system for plasmas in the three-dimensional whole space is shown. The Fokker–Planck–Landau system is a simplification of the Landau equations assuming a linearized, velocity-independent, and isotropic kernel. The resulting equations depend nonlocally and nonlinearly on the moments of the distribution functions via the multispecies local Maxwellians. Furthermore, the existence proof is based on a three-level approximation scheme, energy and entropy estimates, as well as compactness results, and it holds for both soft and hard potentials.

97 MATHEMATICS AND COMPUTING↗

Examining the Impact of Local Constraint Violations on Energy Computations in DFT

ABSTRACT This work examines the impact of locally imposed constraints in Density Functional Theory (DFT). Using a metric referred to as the extent of violation index (EVI), we quantify how well exchange‐correlation functionals adhere to local constraints. Applying EVIs to a diverse set of molecules for GGA functionals reveals constraint violations, particularly for semi‐empirical functionals. We leverage EVIs to explore potential connections between these violations and errors in chemical properties. While no correlation is observed for atomization energies, a significant statistical correlation emerges between EVIs and total energies. Similarly, the analysis of reaction energies suggests weak positive correlations for specific constraints. However, definitive conclusions about error cancellation mechanisms cannot be made at this time. These observations revealed by EVIs may be useful for consideration when designing future generations of semilocal functionals.

Khanna, Vaibhav [Department of Chemistry Universit↗

Quasiparticle and Optical Properties of Carrier-Doped Monolayer MoTe 2 from First Principles

The intrinsic weak and highly nonlocal dielectric screening of two-dimensional materials is well-known to lead to high sensitivity of their optoelectronic properties to environment. Less studied theoretically is the role of free carriers in those properties. In this report we use ab initio GW and Bethe-Salpeter equation calculations, with a rigorous treatment of dynamical screening and local-field effects, to study the doping dependence of the quasiparticle and optical properties of a monolayer transition-metal dichalcogenide, 2H MoTe 2 . Here we predict a quasiparticle band gap renormalization of several hundreds of meV for experimentally attainable carrier densities and a similarly sizable decrease in the exciton binding energy. This results in an almost constant excitation energy for the lowest-energy exciton resonance with an increasing doping density. Using a newly developed and generally applicable plasmon-pole model and a self-consistent solution of the Bethe-Salpeter equation, we reveal the importance of accurately capturing both dynamical and local-field effects to understand detailed photoluminescence measurements.

2D material↗

On Projection of Safe Operation for Grid-Following Inverters - Grid Parameter Estimation

This work investigates the projection of safe operation for grid-following inverters using a reference model. This work applies recursive-least square and model reference adaptive estimation techniques to estimate the unknown grid parameters. The estimated grid parameters are used in a dynamic reference model to project the safe operation of the inverter. This work also demonstrates that the controller nonlinearity and parameter variations can cause unsafe operations, such as unexpected instability at low power levels, namely hidden mode of instability. This instability issue in the nominal operating range may occur for given control parameters in a weak-grid condition. The dynamic reference model for PQ-controlled inverters is applied to analyze this instability issue using the estimated grid parameters. Both adaptive identification techniques can estimate the unknown parameters accurately, and the dynamic reference model can safeguard inverters from an unsafe operation, i.e., hidden instability, by examining the incoming new power setpoints before engaging them to the local controller. The findings are experimentally verified using a small-scale two-level 208 V, 5 kVA inverter feeding a 12 kW NHR 9410 power grid emulator.

Hossen, Tareq↗

Wood Decomposition: Understanding Processes Regulating Carbon Transfer to Soil Carbon Pools Using FACE Wood at Multiple Scales

Dead wood comprises approximately 20% of forest biomass. While it is widely recognized for its role in ecosystem functions relative to habitat and nutrient cycling, there are considerable uncertainties associated with its role in the forest carbon (C) cycle. The principal uncertainty is whether dead wood contributes to the soil C pool. With little supporting evidence, the presumption is that C in wood is respired back to the atmosphere through decomposition processes. The inability to attribute forest soil C to its source components has been a barrier to addressing this important forest carbon cycle question. The U.S. Dept. of Energy’s Free Air CO 2 Enrichment (FACE) experiment produced wood that has a distinct δ 13 C signature that can be used to trace its fate through organic matter decomposition processes. Using two hardwood species (aspen, birch) from the Rhinelander FACE site and pine from the Duke FACE site, the FACE Wood Decomposition Experiment (FWDE) was established in 2011 to provide the foundation for addressing wood decomposition and its associated processes at the continental scale. Plots were installed on nine experimental forests representing a range in bioclimatic forest conditions within the continental U.S. Each identical plot has logs of the three species incubating on the soil surface and pine logs suspended in the air, representing standing dead wood. Abiotic conditions are monitored continuously, and soil and forest conditions characterized. Logs on the sites have been measured every two years to assess decay. This project was initiated in 2016 with specific objectives to: (a) determine whether dead wood C contributes to the soil C pool, (b) assess the fungal community composition mediating the decay, (c) assess the interactions of termites with microbial decay, and (d) develop a mechanistic model to simulate wood decomposition. The principal field sampling was conducted in 2017; correspondingly, the results reported here represent six years of decomposition. Wood decomposition varied from 13 to 75 % loss across the bioclimatic gradient. Sites in the southeastern U.S. coastal plain and piedmont had fastest decomposition rates for each of the species. In contrast sites in the Rocky Mountains had the slowest decay rates, which were associated with cold temperatures. Standing deadwood decomposes at a much slower rate than logs on the soil surface; a response due to differences in wood moisture content. Wood carbon was measured in the mineral soil across each of the sites; accordingly, this is the first study to affirm that a portion of the wood C does become part of the soil C pool. Averaged across the FWDE sites, approximately 1.4% of the soil C in the upper 10 cm of the mineral soil directly beneath the log was derived from the deadwood; within 50 cm of the log, wood C accounted for an average of 2.1%. These results demonstrate that the contribution of deadwood to the soil C pool is a soil volume surrounding the log; and it’s likely a larger volume than what we sampled. We also hypothesized that there would be more wood C in the mineral soil when termites were present. However, that hypothesis wasn’t supported by measurements on the Santee Experimental Forest termite exclusion (SEF-TX) plots under FACE logs that incubated for 6 years. Across all the sites, the majority of the wood C was transferred to the atmosphere. Approximately 7,000 fungal species were sequenced. The fungal communities were different among each of the sites suggesting local colonization; interestingly, within sites the three species also exhibited differences in fungal community composition. White rot was the dominant fungal form in pine and hardwood, which yields less lignin in the wood residue. Brown rot occurred in approximately 20% of the pine and aspen logs, and it did not occur in birch logs. The occurrence of brown rot was only weakly correlated to site factors. We conducted two additional experiments to assess the effects of termites on wood decomposition and the associated interactions with the fungal community. Pine and birch logs were incubated on the Santee Experimental Forest termite exclusion plots in upland and riparian settings. There was no difference in decay between areas where termites were able colonize and plots where they had been excluded. Highly variable foraging by termites was a primary contributor the result. Correspondingly, fungal communities did not vary on logs incubated among the two treatments, but they did reflect site and species differences. The second experiment was conducted on each of the nine FWDE sites where pine and birch wood blocks were incubated for two years with and without a wrapping designed to exclude termites and other arthropods. The effects of termites on wood decomposition could be confirmed on two of the four sites known to have subterranean termites. On the two southeastern sites, termites contributed approximately 8% to mass loss in pine blocks over two years. A major factor clouding the role of termites in wood decomposition is the inability to assess the time, duration, and intensity of the foraging with the logs. Another uncertainty is related to whether a piece of wood will be foraged. A process-based wood decomposition model was developed representing biological processes mediated by fungi, bacteria, termites, beetles, as well as physical and chemical processes. The Coarse Wood Decomposition Model (CWDM) was parameterized based on a thorough review of the literature and it was validated using data from the FWDE. In the initial setup, the model considers softwoods and hardwoods groups, as opposed to individual species. Sensitivity analyses incorporating climate data from 89 locations in North America demonstrated that CWDM was stable from the tropics to the boreal zone. Model calibration and validation showed it to perform very well. The CWDM is poised for additional testing with subsequent FWDE data as well as other data sets, and it is available for incorporation into forest biogeochemical models or DOEs Earth System Modeling framework.

54 ENVIRONMENTAL SCIENCES↗

Weak Form Scientific Machine Learning: Test Function Construction for System Identification

Weak form Scientific Machine Learning (WSciML) is a recently developed framework for data-driven modeling and scientific discovery. It leverages the weak form of equation error residuals to provide enhanced noise robustness in system identification via convolving model equations with test functions, reformulating the problem to avoid direct differentiation of data. The performance, however, relies on wisely choosing a set of compactly supported test functions. In this work, we mathematically motivate a novel data-driven method for constructing Single-scale-Local reference functions for creating the set of test functions. Our approach numerically approximates the integration error introduced by the quadrature and identifies the support size for which the error is minimal, without requiring access to the model parameter values. Through numerical experiments across various models, noise levels, and temporal resolutions, we demonstrate that the selected supports consistently align with regions of minimal parameter estimation error. We also compare the proposed method against the strategy for constructing Multi-scale-Global (and orthogonal) test functions introduced in our prior work, demonstrating the improved computational efficiency.

FOS: Computer and information sciences↗

Local Environment of Superoxide Radical Formed on the TiO 2 Surface Produced From Ti(OiPr) 4 Exposed to H 2 O 2

A selective heterogeneous catalyst with the superoxide anion O 2 •– stable at room temperature, generated by treating Ti(OR) 4 (R=iPr, nBu) with H 2 O 2 , was previously reported and used for the oxidation of organic compounds. Furthermore, it was proposed that exceptional stability of the O 2 •– is resulted from its stabilization near Ti +4 cation on the TiO 2 surface with participation of water molecules and/or OH groups. In this article, we performed high-resolution pulsed EPR study on the O 2 •– in this catalyst with the aim to obtain quantitative information about its interactions with the surrounding molecules. Our data has shown that the O 2 •– is involved in weak hyperfine interactions with protons in the nearest environment, which do not exceed a value of 2 MHz. It corresponds to an Os…H distance of ≥ 3 Å that exclude the formation of hydrogen bonds. The analysis of possible structures of O 2 •– adsorption on TiO 2 surface taking into account our results and lack of radical mobility at room temperature previously observed in EPR spectra led us to suggest that the O 2 •– is stabilized in the form of superoxo bridge coordinated with two titanium atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗