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At least 577 records · Page 32

Density Measurements in Air by Optically Exciting the Cordes Bands of I2

We describe an optical method based on laser-induced fluorescence for obtaining instantaneous measurements of density along a line in low-density air seeded with I2. The Cordes bands of I2 (D(sup 1)sigma(sup +, sub u)) left arrow X(sup 1)sigma(sup +, sub g)) are excited with a tunable ArF excimer laser. air densities in the range (0.1-6.5) x 10(exp 17) cm(exp -3) are measured over 295-583 K using the density-dependent emission ratio of two emission bands of I2; the 340 nm bands and the diffuse-structured McLennan bands near 320 nm.

Balla, R. Jeffrey↗

Fracture and Stress Evolution on Europa: New Insights Into Fracture Interpretation and Ice Thickness Estimates Using Fracture Mechanics Analyses

The work completed during the funding period has provided many important insights into fracturing behavior in Europa's ice shell. It has been determined that fracturing through time is likely to have been controlled by the effects of nonsynchronous rotation stresses and that as much as 720 deg of said rotation may have occurred during the visible geologic history. It has been determined that there are at least two distinct styles of strike-slip faulting and that their mutual evolutionary styles are likely to have been different, with one involving a significant dilational component during shear motion. It has been determined that secondary fracturing in perturbed stress fields adjacent to older structures such as faults is a prevalent process on Europa. It has been determined that cycloidal ridges are likely to experience shear stresses along the existing segment portions as they propagate, which affects propagation direction and ultimately induces tailcracking at the segment tip than then initiates a new cycle of cycloid segment growth. Finally, it has been established that mechanical methods (e.g., flexure analysis) can be used to determine the elastic thickness of the ice shell, which, although probably only several km thick, is likely to be spatially variable, being thinner under bands but thicker under ridged plains terrain.

Kattenhorn, Simon↗

High-throughput computation of electric polarization in solids via Berry flux diagonalization

Electric polarization in the absence of an externally applied electric field is a key property of polar materials, but the standard interpolation-based ab initio approach to compute polarization differences within the modern theory of polarization presents challenges for automated high-throughput calculations. Berry flux diagonalization [J. Bonini et al., Phys. Rev. B 102, 045141 (2020)] has been proposed as an efficient and reliable alternative, though it has yet to be widely deployed. Here, we assess Berry flux diagonalization using ab initio calculations of a large set of materials, introducing and validating heuristics that ensure branch alignment with a minimal number of intermediate interpolated structures. Our automated implementation of Berry flux diagonalization succeeds in cases where prior interpolation-based workflows fail due to band-gap closures or branch ambiguities. Benchmarking with ab initio calculations of 176 candidate ferroelectrics, we demonstrate the efficacy of the approach on a broad range of insulating materials and obtain accurate effective polarization values with fewer interpolated structures than prior automated interpolation-based workflows. Our real-space heuristics that can predict gauge stability a priori from ionic displacements enable a general automated framework for reliable polarization calculations and efficient high-throughput screening of chemically and structurally diverse polar insulators. These results establish Berry flux diagonalization as a robust and efficient method to compute the effective polarization of solids and to accelerate the data-driven discovery of functional polar materials.

Poteshman, Abigail N. [University of Chicago, IL (↗

Chern numbers of topological phonon band crossing determined with inelastic neutron scattering

Topological invariants in the band structure, such as Chern numbers, are important for the understanding and classification of the topological properties of matter and dictate the occurrence of exotic behaviors, yet their direct spectroscopic determination has been largely limited to electronic bands. Here, we use inelastic neutron scattering in conjunction with ab initio calculations to identify a variety of topological phonon band crossings in MnSi and CoSi single crystals. We find a distinct relation between the Chern numbers of a band-crossing node and the scattering intensity modulation in momentum space around the node. Given sufficiently high resolution, our method can be used to determine arbitrarily large Chern numbers of topological phonon band-crossing nodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

𝐵⁡(𝐸⁢2) measurements in the yrast band of 28 Mg: Implications for the 𝑁 = 20 island of inversion

High-precision lifetime measurements in 28 Mg were performed to study neutron shell evolution in Mg isotopes and the onset of the N = 20 island of inversion. Here, using both the recoil distance and Doppler shift attenuation methods, five lifetimes were measured in addition to six upper limits. The observation of two long-lived, negative-parity states demonstrate the importance of studying Mg isotopes for the contribution of intruder configurations to sd-shell nuclei. Lifetimes of the $2^+_1$ and $4^+_1$ states of 1.81(5) ps and 172⁢($^{+11}_{–10}$) stat.⁢ (4) stop. ⁢(8) feed.⁢ (4) targ. fs, respectively, demonstrate a loss of collectivity with increasing spin in the yrast band, permitting for distinguishing between current theoretical models. These measurements also highlight the progression of yrast structure across the Mg isotopic chain from rotational at N = 12 to large shape mixing at N = 16 and back to collective behavior at N = 20 but with dominating intruder configurations.

20 ≤ A ≤ 38↗

Deconstructing the Spectrum of the Soft X-ray Background

The soft X-ray background in the 0.1-1.0 keV band is known to be produced by at least three sources; the Local Hot Bubble (LHB), the extragalactic power law (EPL), and a seemingly galactic component that lies outside the bulk of the absorption that is due to the ISM of the galactic disk. This last component, which we call the Trans-Absorption Emission (TAE), has been modeled by a number of groups who have derived disparate measures of its temperature. The differences have arisen from differing assumptions about the structure of the emitting gas and unrecognized methodological difficulties. In particular, spectral fitting methods do not uniquely separate the TAE from the foreground emission that is due the LHB. This "degeneracy" can be resolved using the angular variation of the absorption of the TAE. We show that the TAE cannot be characterized by a single thermal component; no single-component model can be consistent with both the spectral energy distribution of the TAE emission and the angular variation due to absorption by the galactic disk. We use the angular anticorrelation of the ROSAT All-Sky Survey with the galactic absorption to separate local from distant emission components, and to fit the spectral energy distribution of the resulting distant emission. We find that the emission is best described by a two-thermal-component model with logT(sub S) = 6.06(sup +0.14, sub -0.12) and log T(sub H) = 6.42(sup +0.14, sub -0.12). This two-thermal-component TAE fits the ROSAT spectral energy distribution significantly better than single-component models, and is consistent with both angular variation and spectral constraints.

Kuntz, K. D.↗

Lattice and electronic structure of ScN observed by angle-resolved photoemission spectroscopy measurements

Scandium nitride (ScN) has recently attracted much attention for its potential applications in thermoelectric energy conversion, as a semiconductor in epitaxial metal/semiconductor superlattices, as a substrate for GaN growth, and alloying it with AlN for 5G technology. This study was undertaken to better understand its stoichiometry and electronic structure. ScN (100) single crystals 2 mm thick were grown on a single crystal tungsten (100) substrate by a physical vapor transport method over a temperature range of 1900–2000 °C and a pressure of 20 Torr. The core level spectra of Sc 2p 3/2,1/2 and N 1s were obtained by x-ray photoelectron spectroscopy (XPS). The XPS core levels were shifted by 1.1 eV toward higher values as the [Sc]:[N] ratio varied from 1.4 at 1900 °C to ~1.0 at 2000 °C due to the higher binding energies in stoichiometric ScN. Angle-resolved photoemission spectroscopy measurements confirmed that ScN has an indirect bandgap of ~1.2 eV.

42 ENGINEERING↗

Source of Bright Near-Infrared Luminescence in Gold Nanoclusters

Gold nanoclusters with near-infrared (NIR) photoluminescence (PL) have great potential as sensing and imaging materials in biomedical and bioimaging applications. In this work, Au 21 (S-Adm) 15 and Au 38 S 2 (S-Adm) 20 are used to unravel the underlying mechanisms for the improved quantum yields (QY), large Stokes shifts and long PL lifetimes in gold nanoclusters. Both nanoclusters show decent PL QY. In particular, the Au 38 S 2 (S-Adm) 20 nanocluster shows a bright NIR PL at 900 nm with QY up to 15% in normal solvents (such as toluene) at ambient conditions. The relatively lower QY for Au 21 (S-Adm) 15 (4%) compared to Au 38 S 2 (S-Adm) 20 is attributed to the lowest-lying excited state being symmetry-disallowed, as evidenced by the pressure-dependent anti-spectral shift of the absorption spectra compared to PL. Yet, Au 21 (S-Adm) 15 maintains some emissive properties due to a nearby symmetry-allowed excited state. Furthermore, our results show that suppression of non-radiative decay due to the surface “lock rings” which encircle the Au kernel and the surface “lock atoms” which bridge the fundamental Au-kernel units (e.g., tetrahedra, icosahedra, etc.) is the key to obtain high QYs in gold nanoclusters. Here, the complicated excited-state processes and the small absorption coefficient of the band-edge transition lead to the large Stokes shifts and the long PL lifetimes that are widely observed in gold nanoclusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Oxidation of Metal–Catechol Complexes as a New Synthesis Route to the High-Quality Ternary Photoelectrodes: A Case Study of Fe 2 TiO 5 Photoanodes

A new electrochemical, solution-based synthesis method to prepare uniform multinary oxide photoelectrodes was developed. This method involves solubilizing multiple metal ions as metal-catechol complexes in a pH condition where they are otherwise insoluble. When some of the catechol ligands are electrochemically oxidized, the remaining metal complexes become insoluble and are deposited as metal-catechol films on the working electrode. The resulting films are then annealed to form crystalline multinary oxide electrodes. Since catechol can serve as a complexing agent for a variety of metal ions, the newly developed method can be used to prepare a variety of multinary oxide films. In the present study, we used this method to prepare n-type Fe 2 TiO 5 photoanodes and investigated their photoelectrochemical properties for use in a photoelectrochemical water splitting cell. We also performed a computational investigation with two goals. The first goal was to investigate small electron polaron formation in Fe 2 TiO 5 . Charge transport in most oxide photoelectrodes involves small polaron hopping, but small polaron formation in Fe 2 TiO 5 has not been examined prior to this work. The second goal was to investigate the effect of substitutional Sn doping at the Fe site on the electronic band structure and the carrier concentration of Fe 2 TiO 5 . Here, the combined experimental and theoretical results presented in this study greatly improve our understanding of Fe 2 TiO 5 for use as a photoanode.

14 SOLAR ENERGY↗

Atomic-Site-Specific Surface Valence-Band Structure from X-Ray Standing-Wave Excited Photoemission

X-ray standing-wave (XSW) excited photoelectron emission was used to measure the site-specific valence band (VB) for ½ monolayer (ML) Pt grown on a SrTiO 3 (001) surface. The XSW induced modulations in the core level (CL), and VB photoemission from the surface and substrate atoms were monitored for three ℎ⁡kl substrate Bragg reflections. The XSW CL analysis shows the Pt to have a face-centered-cubic-like cube-on-cube epitaxy with the substrate. The XSW VB information compares well to a density functional theory calculated projected density of states from the surface and substrate atoms. Altogether, this Letter represents a novel method for determining the contribution to the density of states by valence electrons from specific atomic surface sites.

74 ATOMIC AND MOLECULAR PHYSICS↗

Toward Mass-Production of Transition Metal Dichalcogenide Solar Cells: Scalable Growth of Photovoltaic-Grade Multilayer WSe2 by Tungsten Selenization

Semiconducting transition metal dichalcogenides (TMDs) are promising for high-specific-power photovoltaics due to their desirable band gaps, high absorption coefficients, and ideally dangling-bond-free surfaces. Despite their potential, the majority of TMD solar cells to date are fabricated in a nonscalable fashion, with exfoliated materials, due to the lack of high-quality, large-area, multilayer TMDs. Here, we present the scalable, thickness-tunable synthesis of multilayer WSe2 films by selenizing prepatterned tungsten with either solid-source selenium at 900 degrees C or H2Se precursors at 650 degrees C. Both methods yield photovoltaic-grade, wafer-scale WSe2 films with a layered van der Waals structure and superior characteristics, including charge carrier lifetimes up to 144 ns, over 14x higher than those of any other large-area TMD films previously demonstrated. Simulations show that such carrier lifetimes correspond to ~22% power conversion efficiency and ~64 W g-1 specific power in a packaged solar cell, or ~3 W g-1 in a fully packaged solar module. The results of this study could facilitate the mass production of high-efficiency multilayer WSe2 solar cells at low cost.

carrier lifetime↗

Evolution of the Electronic Gap of Directly Synthesized Versus Mechanically Transferred WS 2 Monolayer to Multilayer Films

The electronic properties of 2D materials play a critical role in determining their potential for device applications. Despite rapid developments in 2D semiconductors, studies of fundamental electronic parameters, including the electronic gap and ionization energy, are limited, with significant discrepancies in reported values. The study focuses on tungsten disulfide (WS₂) and investigates the electronic structure of films comprising an increasing number of layers deposited with two different methods: direct synthesis via metal–organic chemical vapor deposition (MOCVD) and additive mechanical transfer of exfoliated single layers. The films are characterized via Raman, UV–vis, and photoluminescence spectroscopies, as well as ultraviolet photoelectron and inverse photoemission spectroscopies (UPS/IPES). The electronic gap of WS₂ is found to decrease from 2.43 eV for the monolayer to 1.97 eV for the trilayer, indicating a bulk transition at the trilayer thickness. This reduction in the electronic gap is primarily due to the downward shift of the conduction band minimum relative to the valence band maximum. A comparative analysis with MOCVD-grown WS₂ reveals a slightly larger electronic gap for MOCVD-grown samples, attributed to differences in defect densities. The electronic levels evaluated through UPS/IPES highlight the significant influence of preparation methods on the electronic properties of WS₂.

2D materials↗

ARCADE 2 Observations of Galactic Radio Emission

We use absolutely calibrated data from the Absolute Radiometer for Cosmology, Astrophysics, and Diffuse Emission (ARCADE 2) flight in July 2006 to model Galactic emission at frequencies 3, 8, and 10 GHz. The spatial structure in the data is consistent with a superposition of free-free and synchrotron emission. Emission with spatial morphology traced by the Haslam 408 MHz survey has spectral index beta_synch = -2.5 +/- 0.1, with free-free emission contributing 0.10 +/- 0.01 of the total Galactic plane emission in the lowest ARCADE 2 band at 3.15 GHz. We estimate the total Galactic emission toward the polar caps using either a simple plane-parallel model with csc|b| dependence or a model of high-latitude radio emission traced by the COBE/FIRAS map of CII emission. Both methods are consistent with a single power-law over the frequency range 22 MHz to 10 GHz, with total Galactic emission towards the north polar cap T_Gal = 0.498 +/- 0.028 K and spectral index beta = -2.55 +/- 0.03 at reference frequency 0.31 GHz. The well calibrated ARCADE 2 maps provide a new test for spinning dust emission, based on the integrated intensity of emission from the Galactic plane instead of cross-correlations with the thermal dust spatial morphology. The Galactic plane intensity measured by ARCADE 2 is fainter than predicted by models without spinning dust, and is consistent with spinning dust contributing 0.4 +/- 0.1 of the Galactic plane emission at 23 GHz.

Kogut, A.↗

NASA/ONERA Collaboration on Small Hovering Rotor Broadband Noise Prediction using Lattice-Boltzmann and Structured Navier-Stokes Solvers

This work compares two lattice-Boltzmann method solvers, PowerFLOW and ProLB, and two structured Navier-Stokes solvers, OVERFLOW2 and FAST, used by NASA and ONERA, respectively, for the broadband noise prediction of an ideally twisted rotor as part of Implementing Arrangement number FR-0685-0, ‘Comparing Computational Fluid Dynamics Solvers for Broadband Noise Prediction.’ Predicted results are evaluated against measured data from both smooth and rough blade sets acquired in the Small Hover Anechoic Chamber at the NASA Langley Research Center. Aerodynamic thrust predictions are seen to agree more favorably with the rough-blade measurements, whereas torque predictions agree better with the smooth-blade measurements. A tonal noise comparison shows better agreement to the measured data with the two structured Navier-Stokes solvers than with the two lattice-Boltzmann solvers, which is thought to be caused by the different geometric discretization associated with each solver paradigm. Broadband noise comparisons show that both lattice-Boltzmann method solvers trend well with the smooth-blade measurements, with the exception of an overprediction by ProLB between 4 kHz and 15 kHz. OVERFLOW2 is seen to capture the measured nondeterministic tonal content between 3 kHz and 8 kHz on a narrowband spectral basis and FAST agrees well with the rough blades on a one-third octave band basis.

Christopher S. Thurman↗

Optical constants of polycrystalline Al 0.25 Ga 0.75 P and Al 0.9 Ga 0.1 As determined by variable-angle spectroscopic ellipsometry

The optical constants of single-crystal Al x Ga 1-x P and Al x Ga 1-x As have been widely studied at various Al compositions but have not yet been thoroughly investigated as polycrystalline materials. Using variable-angle spectroscopic ellipsometry, we estimate and analyze the optical constants of polycrystalline Al 0.25 Ga 0.75 P and Al 0.9 Ga 0.1 As that were non-epitaxially deposited at deposition temperatures of either 250 or 420 °C, and with various dopant species, dopant concentrations, and V/III flux ratios. Here, for wavelengths of 350–400 nm, decreasing the V/III ratio increases the refractive index of Be-doped polycrystalline Al 0.25 Ga 0.75 P. For wavelengths >500 nm, as the targeted Be dopant concentration increases for polycrystalline Al 0.25 Ga 0.75 P, the amount the extinction coefficient increases and the indirect bandgap decreases depends on the V/III ratio. Furthermore, Si-doped polycrystalline Al 0.25 Ga 0.75 P has significantly smaller extinction coefficient values than when it is Be-doped, for the same V/III ratio and targeted doping concentration, at wavelengths >500 nm. Based on our findings, we hypothesize that the dopant species, dopant concentration, and the V/III ratio dictate various types of defect concentrations, which then affect the optical constants and indirect bandgap of polycrystalline Al 0.25 Ga 0.75 P. Additionally, for wavelengths >500 nm, we find that polycrystalline Al 0.25 Ga 0.75 P and Al 0.9 Ga 0.1 As have the lowest extinction coefficient values when deposited at 420 °C, as opposed to 250 °C. Thus, we hypothesize that the deposition temperature is the most significant factor in dictating the optical constants of these polycrystalline III-Vs. Ultimately, this work demonstrates alternative methods to tune the optical constants of polycrystalline Al 0.25 Ga 0.75 P and Al 0.9 Ga 0.1 As, as opposed to tuning the Al composition.

42 ENGINEERING↗

The Dynamical Role of Optical Phonons and Sublattice Screening in a Solid-State Ion Conductor

Solid-state electrolytes (SSEs) require ionic conductivities that are competitive with liquid electrolytes to realize applications in all-solid-state batteries. Although candidate SSEs have been discovered, the underlying mechanisms enabling superionic conduction (>1 mS cm –1 ) remain elusive. In particular, the role of ultrafast lattice dynamics in mediating ion migration, which involves couplings between ions, phonons, and electrons, is rarely explored experimentally at their corresponding time scales. To investigate the complex contributions of coupled lattice dynamics on ion migration, we modulate the charge density occupations within the crystal framework and then measure the time-resolved change in impedance on picosecond time scales for a candidate SSE, Li 0.5 La 0.5 TiO 3 (LLTO). Upon perturbation, we observe enhanced ion migration at ultrafast time scales. The respective transients match the time scales of optical and acoustic phonon vibrations, suggesting their involvement in ion migration. We further computationally evaluate the effect of a charge transfer from the O 2p to the Ti 3d band on the electronic and physical structure of LLTO. We hypothesize that the charge-transfer excitation distorts the TiO 6 polyhedra by altering the local charge density occupancy of the hopping site at the migration pathway saddle point, thereby causing a reduction in the migration barrier for the Li + hop. We rule out the contribution of photogenerated electron carriers and laser heating. Overall, our investigation introduces a new spectroscopic tool to probe fundamental ion hopping mechanisms transiently at ultrafast time scales, which has previously only been achieved in a time-averaged manner or solely via computational methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

VarIabiLity seLection of AstrophysIcal sources iN PTF (VILLAIN): I. Structure function fits to 71 million objects

Light-curve variability is well-suited to characterizing objects in surveys with high cadence and a long baseline. This is especially relevant in view of the large datasets to be produced by the Vera C. Rubin Observatory Legacy Survey of Space and Time (LSST). We aim to determine variability parameters for objects in the Palomar Transient Factory (PTF) and explore differences between quasars (QSOs), stars, and galaxies. We relate variability and colour information in preparation for future surveys. We fit joint likelihoods to structure functions (SFs) of 71 million PTF light curves with a Markov chain Monte Carlo method. For each object, we assume a power-law SF and extract two parameters: the amplitude on timescales of one year, A, and a power-law index, γ. With these parameters and colours in the optical (Pan-STARRS1) and mid-infrared (WISE), we identify regions of parameter space dominated by different types of spectroscopically confirmed objects from SDSS. Candidate QSOs, stars, and galaxies are selected to show their parameter distributions. QSOs show high-amplitude variations in the R band, and the highest γ values. Galaxies have a broader range of amplitudes and their variability shows relatively little dependency on timescale. With variability and colours, we achieve a photometric selection purity of 99.3% for QSOs. Even though hard cuts in monochromatic variability alone are not as effective as seven-band magnitude cuts, variability is useful in characterizing object subclasses. Through variability, we also find QSOs that were erroneously classified as stars in the SDSS. We discuss perspectives and computational solutions in view of the upcoming LSST.

79 ASTRONOMY AND ASTROPHYSICS↗

Active learning approach to simulations of strongly correlated matter with the ghost Gutzwiller approximation

Quantum embedding (QE) methods such as the ghost Gutzwiller approximation (gGA) offer a powerful approach to simulating strongly correlated systems, but come with the computational bottleneck of computing the ground state of an auxiliary embedding Hamiltonian (EH) iteratively. In this work, we introduce an active learning (AL) framework integrated within the gGA to address this challenge. The methodology is applied to the single-band Hubbard model and results in a significant reduction in the number of instances where the EH must be solved. Through a principal component analysis (PCA), we find that the EH parameters form a low-dimensional structure that is largely independent of the geometric specifics of the systems, especially in the strongly correlated regime. Our AL strategy enables us to discover this low-dimensionality structure on the fly, while leveraging it for reducing the computational cost of gGA, laying the groundwork for more efficient simulations of complex strongly correlated materials. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗