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At least 523 records · Page 29

Response of the Verwey transition in magnetite to controlled point-like disorder induced by 2.5 MeV electron irradiation

Controlled point-like disorder induced by low temperature 2.5 MeV electron irradiation was used to probe the nature of the Verwey transition in magnetite, Fe 3 O 4 . Two large single crystals, one with optimal transition temperature, T V ≈ 121 K, and another with T V ≈ 109 K, as well as magnetite magnetosome nanocrystals harvested from the lysed cells of the marine magnetotactic vibrio Magnetovibrio blakemorei strain MV-1, T V ≈ 110 K, were examined. Temperature-dependent resistivity is consistent with the semiconductor-to-semiconductor (insulator) sharp, step-like Verwey transition from a state with a small bandgap of around 60 meV to a state with a large bandgap of about 300 meV. The irradiation causes an up-shift of the resistivity curves above the transition without transition smearing or broadening. It also causes an apparent down-shift of the resistivity maximum at high temperatures. In the lower crystal, the electron irradiation drives the transition temperature into a “forbidden” interval of T V , believed to separate the first order from the second order phase transition. Contrary to this belief, the transition itself remains sharp and hysteretic without a significant change in the hysteresis width indicating the strong 1st order character of the Verwey transition for all TV values. The separate 2nd order - looking transition is likely due to sample inhomogeneities. Here we conclude that the sudden change of the bandgap accompanied (or driven) by the monoclinic distortion and the change of magnetic anisotropy is the reason for the Verwey transition in magnetite and the effect of additional disorder is mostly in the smearing of the sharp gap edges near the Fermi level.

36 MATERIALS SCIENCE↗

Analysis of the EMCCD point-source response using x-rays

Electron Multiplying Charge Coupled Devices, EMCCD are used as x-ray detectors. The NSLS-II Soft Inelastic x-ray Scattering (SIX) beam line has two EMCCDs for x-ray detection in the spectrometer arm. The spectrometer with high resolving power disperses x-rays vertically. The x-ray vertical position on the sensor plane is related to its energy. This allows for very accurate x-ray energy measurements through x-ray coordinates. X-rays interact with silicon and create a number of electron-hole pairs proportional to the x-ray energy. Electrons drift and diffuse toward pixel gates and are collected there. The diffused electrons form a charge cloud distributed over several neighboring pixels. This charge sharing enables coordinate measurements with accuracy better than the pixel pitch. The charge distribution shape has to be taken into account to achieve ultimate accuracy in coordinate measurements. In this paper, we present a method of the charge distribution shape analysis and demonstrate its applications. The drift and diffusion of electrons ftom the point of generation to pixel gates results in the bell-shaped electron cloud usually approximated by Gaussian shape. The number of electrons collected under a pixel is proportional to the shape function integral. These electron packets get transferred to the sense node of the output amplifier. The transfer process could introduce distortions to the original charge distribution. For example, during transfers, electrons in the packet could be exposed to traps if they are present in the sensor. The trapping and later the release processes distort the apparent shape of the charge distribution. Therefore, deviations of the charge distribution shape ftom the originally symmetrical form can indicate the presence of trap centers in the sensor and can be used for sensor diagnostics.

47 OTHER INSTRUMENTATION↗

Axion induced SUSY breaking and focus point gaugino mediation

We consider a scenario where supersymmetry breaking, its mediation, and the cancellation of the theta parameter of SU(3) C are all caused by a single chiral multiplet. The string axion multiplet is a natural candidate of such a superfield. We show that the scenario provides a convincing basis of focus point gaugino mediation, where the electroweak scale is explained with a moderate tuning among the parameters of the theory.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

ν-point energy correletors with F AST EEC: Small-x physics from LHC jets

In recent years, energy correlators have emerged as a powerful tool for studying jet substructure, with promising applications such as probing the hadronization transition, analyzing the quark-gluon plasma, and improving the precision of top quark mass measurements. The projected N-point correlator measures correlations between N final-state particles by tracking the largest separation between them, showing a scaling behavior related to DGLAP splitting functions. These correlators can be analytically continued in N, commonly referred to as ν-correlators, allowing access to non-integer moments of the splitting functions. Of particular interest is the ν → 0 limit, where the small momentum fraction behavior of the splitting functions requires resummation. Originally, the computational complexity of evaluating ν-correlators for M particles scaled as 2 2M , making it impractical for real-world analyses. However, by using recursion, we reduce this to M 2M , and through the FastEEC method of dynamically resolving subjets, M is replaced by the number of subjets. This breakthrough enables, for the first time, the computation of ν-correlators for LHC data. In practice, limiting the number of subjets to 16 is sufficient to achieve percent-level precision, which we validate using known integer-ν results and convergence tests for non-integer ν. We have implemented this in an update to FastEEC and conducted an initial study of power-law scaling in the perturbative regime as a function of ν, using CMS Open Data on jets. The results agree with DGLAP evolution, except at small ν, where the anomalous dimension saturates to a value that matches the BFKL anomalous dimension.

Energy correlators↗

Techno-economic comparison of sCO 2 cycles for particle-based CSP at design-point conditions

In this work, we compare the techno-economic performance of supercritical carbon dioxide power cycles integrated in a particle CSP system. We model four core cycle configurations: simple (with optional bypass), recompression (with optional bypass), partial cooling, and turbine split flow, which each demonstrate different benefits in a CSP system, such as high efficiency, low cost, or large HTF temperature differences. We parametrically sweep cycle design variables for each configuration. The set of power cycle performance results are then combined with a design point particle CSP system model which calculates the system specific cost. The simple cycle and turbine split flow cycles have the best performance in the baseline results, with system specific costs of 5,912 and 5,899 $\$$/kWe respectively. In addition to the baseline set of results, we also vary key parameters and costs in a sensitivity study. The cycle designs with the best system performance limit their efficiency to ~45 %, despite demonstrating higher maximum efficiencies, due to the rapid increase in cost of recuperation as efficiencies rise. The simple cycle has strong performance in the analysis and is on average only 1.4 % worse than the optimal configuration. Lowered turbine inlet temperatures from the sensitivity study improve performance by reducing the PHX and turbine cost. Decreasing the inlet temperature from 700 to 625°C results in an >8 % decrease in system specific cost. Future work should expand sensitivity analyses to colder turbine inlet temperatures and calculate system performance by simulating annual performance with off-design solar and cycle component models.

14 SOLAR ENERGY↗

How equation of state selection impacts accuracy near the critical point: Forced convection supercritical CO 2 flow over a cylinder

Increasing application of supercritical fluids leads to increased use of numerical simulations to guide designs. However, the impact of Equations of State (EoS) selection on computational cost and accuracy is not well understood. Laminar flow around a heated cylinder is used as a test case. A robust matrix of 99-simulations is used to analyze the flow of carbon dioxide just above the critical point at the isobaric condition of 8 MPa and temperatures between 305 and 390 K. Four EoS were studied: Ideal Gas Law, cubic EoS’s Peng-Robinson and Soave-Redlich-Kwong, and the Span-Wagner EoS. Results were identical for isothermal cases, but for heated or cooled cases, the high-fidelity Span-Wagner EoS simulations presented drastically different wake structures. Compared to the high-fidelity SW EoS, cEoS’s underestimated Nu values by up to 38% and cEoS’s underestimated CD values by 18–42%. In conclusion, the Span-Wagner EoS required only 17% more computation time then the cubic EoS simulations, making the Span-Wagner EoS recommended for engineering design.

42 ENGINEERING↗

Disinfection byproducts formed during drinking water treatment reveal an export control point for dissolved organic matter in a subalpine headwater stream

Changes in climate, season, and vegetation can alter organic export from watersheds. While an accepted tradeoff to protect public health, disinfection processes during drinking water treatment can adversely react with organic compounds to form disinfection byproducts (DBPs). By extension, DBP monitoring can yield insights into hydrobiogeochemical dynamics within watersheds and their implications for water resource management. In this study, we analyzed temporal trends from a water treatment facility that sources water from Coal Creek in Crested Butte, Colorado. These trends revealed a long-term increase in haloacetic acid and trihalomethane formation over the period of 2005-2020. Additionally, disproportionate export of dissolved organic carbon and formation of DBPs that exceeded regulatory guidelines were consistently recorded in association with late spring freshet. Synoptic sampling of the creek in 2020 and 2021 identified a biogeochemical hotspot for organic carbon export in the upper domain of the watershed that contained a prominent fulvic acid-like fluorescent signature. DBP formation potential analyses from this domain yielded similar ratios of dominant DBP species to those formed at the drinking water facility. Spectrometric qualitative analyses of pre and post-reacted waters with hypochlorite indicated ligninlike and condensed hydrocarbon-like molecules were the major reactive chemical classes during chlorine-based disinfection. This study demonstrates how drinking water quality archives can be coupled with synoptic sampling to identify and understand export control points for dissolved organic matter. Resultant understanding can be applied in water treatment and watershed management plans to improve drinking water quality sourced from analogous watersheds.

47 OTHER INSTRUMENTATION↗

Focused Ion Beam Preparation of Low Melting Point Metals: Lessons Learned From Indium

Indium (In) and other low melting point metals are used as interconnects in a variety of hybridized circuits and a full understanding of the metallurgy of these interconnects is important to the reliability and performance of the devices. Here, this paper shows that room temperature focused ion beam (FIB) preparation of cross-sections, using Ga + or Xe + can result in artifacts that obscure the true In microbump structure. The use of modified milling strategies to minimize the increased local sample temperature are shown to produce cross-sections that are representative of the In bump microstructure in some sample configurations. Furthermore, cooling of the sample to cryogenic temperatures is shown to reliably eliminate artifacts in FIB prepared cross-sections of In bumps allowing the true bump microstructure to be observed.

36 MATERIALS SCIENCE↗

Mo 4 FeGa 17.25– x Ge x : Complementary Point Substitutions, Buffering Frameworks, and Merging of the 18-n and Octet Bonding Schemes

We present the discovery of Mo 4 FeGa 17.25–x Ge x (x ∼ 2.1(4), based on determination of Ge content), a complex gallide featuring a variety of point substitution phenomena. Its crystal structure is derived from the Ti 2 Ni type, in which a diamond network of face-sharing octahedra is interpenetrated by a second diamond network of vertex-sharing stella quadrangula. However, while in the ideal Ti 2 Ni type these two frameworks run uninterrupted through the crystal, Mo 4 FeGa 17.25–x Ge x shows three variations. First, the inner tetrahedron of every other stella quadrangula is replaced with a main group atom, creating tetrahedra reminiscent of the Zintl phase NaTl. Next, a selection of Ga 6 octahedra are filled with Fe atoms, in a manner analogous to the stuffed AuCu 3 -type phases. Finally, the refined crystal structure shows that in each unit cell a single Ga2 atom in the octahedral network is substituted with a dumbbell of Ga/Ge atoms. Electronic structure calculations on ordered models of Mo 4 FeGa 17.25–x Ge x reveal a narrow band near the Fermi energy, which is explained in terms of the 18-n and octet bonding schemes using reversed approximation Molecular Orbital analysis. A DFT-chemical pressure analysis connects the tetrahedron/atom and atom/dumbbell substitutions to the relief of atomic packing tensions and highlights soft atomic motions within the octahedral framework and driving forces for atom/dumbbell substitution. The combination of soft vibrational modes, disorder, and a narrow band gap could make this phase of interest for potential thermoelectric properties.

Chemical structure↗

Evaluation of Uncertainties in the Anthropogenic SO 2 Emissions in the USA from the OMI Point Source Catalog

Satellite remote sensing is a promising method of monitoring emissions that may be missing in inventories, but the accuracy of these estimates is often not clear. We demonstrate here a comprehensive evaluation of errors in anthropogenic sulfur dioxide (SO 2 ) emission estimates from NASA’s OMI point source catalog for the contiguous US by comparing emissions from the catalog with high-quality emission inventory data over different dimensions including size of individual sources, aggregate vs individual source errors, and potential bias in individual source estimates over time. For sources that are included in the catalog, we find that errors in aggregate (sum of error for all included sources) are relatively low. Errors for individual sources in any given year can be substantial, however, with over- or underestimates in terms of total error ranging from –80 to 110 kt (roughly 10–90th percentile). In this study, we find that these errors are not necessarily random over time and that there can be consistently positive or negative biases for individual sources. We did not find any overall statistical relationship between the degree of isolation of a source and bias, either at a 40 or 70 km scales. For a sub-set of sources where inventory emissions over a radius of 70 km around an OMI detection are larger than twice the emissions within 40 km, the OMI value is consistently overestimated. We find, as expected, that emission sources not included in the catalog are the largest aggregate source of difference between the satellite estimates and inventories, especially in more recent years where source emission magnitudes have been decreasing and note that trends in satellite detections do not necessarily track trends in total emissions. We find that the OMI-based SO 2 emissions are accurate in aggregate, when summed over a number of sources, but must be interpreted more cautiously at the individual source level. Similar analyses would be valuable for other satellite emission estimates; however, in many cases, the appropriate high-quality reference data may need to be generated.

54 ENVIRONMENTAL SCIENCES↗

Excited State Properties of Point Defects in Semiconductors and Insulators Investigated with Time-Dependent Density Functional Theory

Here, we present a formulation of spin-conserving and spin-flip hybrid time-dependent density functional theory (TDDFT), including the calculation of analytical forces, which allows for efficient calculations of excited state properties of solid-state systems with hundreds to thousands of atoms. We discuss an implementation on both GPU- and CPU-based architectures along with several acceleration techniques. We then apply our formulation to the study of several point defects in semiconductors and insulators, specifically the negatively charged nitrogen-vacancy and neutral silicon-vacancy centers in diamond, the neutral divacancy center in 4H silicon carbide, and the neutral oxygen-vacancy center in magnesium oxide. Our results highlight the importance of taking into account structural relaxations in excited states in order to interpret and predict optical absorption and emission mechanisms in spin defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin Emitters beyond the Point Dipole Approximation in Nanomagnonic Cavities

Control over transition rates between spin states of emitters is crucial in a wide variety of fields ranging from quantum information science to the nanochemistry of free radicals. We present an approach to drive both electric and magnetic dipole-forbidden transitions of a spin emitter by placing it in a nanomagnonic cavity, requiring a description of both the spin emitter beyond the point dipole approximation and the vacuum magnetic fields of the nanomagnonic cavity with a large spatial gradient over the volume of the spin emitter. We specifically study the silicon vacancy (SiV – ) defect in diamond, whose Zeemansplit ground states comprise a logical qubit for solid-state quantum information processing, coupled to a magnetic nanoparticle serving as a model nanomagnonic cavity capable of concentrating microwave magnetic fields into deeply subwavelength volumes. Through first-principles modeling of the SiV – spin orbitals, we calculate the spin transition densities of magnetic dipole-allowed and -forbidden transitions and calculate their coupling rates to various multipolar modes of the nanomagnonic cavity. We envision using such a framework for manipulation of quantum spin states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of Single-Electron Transport and Charging on Individual Point Defects in Atomically Thin WSe 2

Defects significantly impact the properties of 2D semiconductors, providing in-gap quantum states that can serve as a natural platform for single-electron operations, localization sites for excitons to serve as single-photon sources, and potentially quantum spin memories. To date, however, a microscopic observation of such a single-electron transport (SET) behavior has been rarely reported on single defects of 2D semiconductors. In this study, we report a SET and charge-state transition on individual point-defect states buried in the bilayer WSe 2 using scanning tunneling microscopy. SET characteristics of their states is evidenced by both the Coulomb staircase and the saturation behavior of the transport current, consistent with the SET model. Furthermore, we demonstrate that, through the local field of a scanning tunneling microscope tip, it is possible to successively charge the defects by single electrons, suggested by both the ring structures and charging peaks in dI/dV measurements. Our results provide new insights into the quantum nature of these defect-bound states, as well as the possibility of using their single-electron behavior and response for applications in quantum information and local-field sensing.

2D semiconductor↗

Point Defects Control Guest Molecule Diffusion in the 1D Pores of Zn(tbip)

Molecular diffusion plays a critical role in metal-organic frameworks (MOFs) within the application of kinetic chemical separations. We carefully study in this work the unexpected role of point defects for short-chain alkanes diffusing in Zn(tbip), an MOF with rigid one-dimensional (1D) channels. Inside a defect-free Zn(tbip), guest molecules are expected to follow single-file diffusion along 1D channels. It has been found previously by Heinke et al. that these parallel 1D channels are connected for molecular diffusion. Our density functional theory (DFT) calculations suggest that linker vacancy defects could arise under experimentally relevant conditions by removing a pair of linkers. Further climbing-image nudged elastic band (cNEB) DFT calculations indicate that hopping of short-chain alkanes between adjacent 1D channels over defect windows can occur at moderate temperatures. In addition to providing insights into connected adjacent 1D channels in Zn(tbip), Heinke et al. also inferred that most 1D pores are blocked from a microkinetic model. Additionally, we explored the influence of hydrolyzed linker created by the formation of linker removal inside 1D pores. Our DFT calculations show that the linkers can effectively block the pores and the linker diffusion in 1D channels is slow. Our results, for the first time, offer a mechanistic explanation of the unexpected molecular diffusion behavior in this MOF with 1D channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mesostructuring in Liquid–Liquid Extraction Organic Phases Originating from Critical Points

Organic phase structure plays an important role in solute extraction energetics and phase behavior of liquid-liquid extraction (LLE) systems. For a binary extractant (amphiphile)/solvent mixture of relevance to LLE, we find that the organic phase mesostructuring is consistent with extractant concentration fluctuations as the compositional isotherm traverses the Widom line above its liquid-liquid critical point. This reveals a different mechanism for the well-documented heterogeneities in LLE organic phases that are typically attributed to micellization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Point Defects in Two-Dimensional Ruddlesden–Popper Perovskites Explored with Ab Initio Calculations

Two-dimensional Ruddlesden–Popper (RP) halide perovskites stand out as excellent layered materials with favorable optoelectronic properties for efficient light-emitting, spintronic, and other spin-related applications. However, properties often determined by defects are not well understood in these perovskite systems. This work investigates the ground state electronic structure of commonly formed defects in a typical RP perovskite structure by density functional theory. Our study reveals that these 2D perovskites generally retain their defect tolerance with limited perturbation of the electronic structure in the case of neutral-type point defects. In contrast, donor/acceptor defects induce deep midgap states, potentially causing harm to the material’s electronic performance. To retain positive intrinsic properties, the halide vacancies and interstitial defects should be avoided. The observed strong electron localization results in trap states and consequently leads to reduced device performance. Finally, this understanding can guide experimental efforts that aim for improved 2D halide perovskite-based device performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quasinormal Coupled-Mode Analysis of Dynamic Gain in Exceptional-Point Lasers

One of the key features of lasers operating near exceptional points (EPs) is that the gain medium can support an oscillating population inversion above a pump threshold, leading to self-modulated laser dynamics. This unusual behavior opens up new possibilities for frequency comb generation and temporal modulation. However, the dynamic population inversion couples signals with different frequencies and is difficult to capture using conventional temporal coupled-mode theory (TCMT) based on stationary saturable gain. In this paper, we develop a perturbative coupled-mode analysis framework to capture the spatial-temporal dynamics of near-EP lasers. By decomposing discrete frequency generation into multiple excitations of resonant modes, our analysis establishes a minimal physical model that translates the local distribution of dynamic population-inversion into a resonant modal interpretation of laser gain. Furthermore, this work enables the exploration of unique properties in this self-time-modulated systems, such as time-varying scattering and nonreciprocal transmission.

Absorption↗

Distribution Cutoff for Clusters near the Gel Point

The mechanical and dynamic properties of developing networks near the gel point are susceptible to the distribution of clusters coexisting with percolating networks. The distribution of cluster numbers follows a broad power law, wrapped by a cutoff function that rapidly decays at a characteristic size. The form of the cutoff function has been speculated based on known results from lattice percolation and, in certain cases, solved. We obtained this cutoff function from simulated dynamic clusters of polymeric precursor chains using a hybrid Monte Carlo algorithm. The results obtained from three different precursor chain lengths are consistent with each other and are consistent with the expectation from lattice percolation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗