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At least 379 records · Page 21

Strontium Tris(cyclopentadienyl) Complexes: Isostructural f0/d0 Analogues of Divalent Lanthanides

Isostructural, diamagnetic diluents are commonly used in magnetic investigations to eliminate interactions between neighboring electron spins. For divalent lanthanides, these diluents are currently limited to closed-shell ytterbium(II) complexes; ytterbium(II), however, is a poor size-match for the large early- and mid-lanthanides, precluding access to certain ligand frameworks. To aid in the study of lanthanide(II) complexes with unconventional electronic structures and magnetic properties, three strontium tris-cyclopentadienyl complexes, [K(2.2.2-cryptand)][SrCpR3], with common substituted cyclopentadienyl ligands, CpR = C5Me4H (Cptet), C5H4(SiMe3) (Cp'), and C5H3(SiMe3)2 (Cp″) were synthesized, characterized, and examined as diamagnetic diluents. En route to their synthesis, two new Sr metallocenes, [SrCpR2] CpR = Cptet, Cp', were also prepared. [K(2.2.2-cryptand)][SrCptet3] was used to dilute the new complex [K(2.2.2-cryptand)][EuIICptet3], and the EPR spectra of the diluted material shows narrower linewidths than those of pure [K(2.2.2-cryptand)][EuIICptet3], suggesting an increase in the spin-spin relaxation time that enables determination of the europium hyperfine coupling constant.

Zlotnikov, Samuel B↗

Hopping frustration-induced flat band and strange metallicity in a kagome metal

The introduction of localized electronic states into a metal can alter its physical properties, for example enabling exotic metal physics including heavy fermion and strange metal behaviour. A common source of localized states in such systems are partially filled 4f and 5f shells because of the inherently compact nature of those orbitals. The interaction of electrons in these orbitals with the conduction sea is well described by the Kondo framework. However, there have also been observations of Kondo-like behaviour in 3d transition metal oxides and in 4d- and 5d-containing van der Waals heterostructures. This calls for a broader consideration of the physical requirements for Kondo systems. Here we show transport and thermodynamic hallmarks of heavy fermion and strange metal behaviour that arise in the kagome metal Ni3In, wherein the source of localized states is destructive interference-induced band flattening of partially filled Ni 3d states. With magnetic field and pressure tuning, here we also find evidence that the system is proximate to quantum criticality, extending the analogy to f-electron Kondo lattices. These observations highlight the role of hopping frustration in metallic systems as a potential source for strong correlations. Additionally, this suggests a lattice-driven approach to realizing correlated metals with non-trivial band topology.

36 MATERIALS SCIENCE↗

Observations of odd-half cyclotron harmonic emissions in a shell-Maxwellian laboratory plasma

During the last 14 years, the subject of odd-half electron cyclotron harmonic emission from plasma has been given considerable attention. It was apparently first reported to occur in a beam plasma machine. The existence of the emission in space has been well documented through observations made with satellites. Because wavelengths are difficult to observe in space, no wave number spectrum has ever been obtained for the half-odd harmonic emission. Such a spectrum together with a frequency spectrum might provide the basis for a successful modeling of the instability. The present investigation is concerned with the design of a laboratory experiment in which a plasma with an anisotropic velocity distribution is produced and measured. In addition, the dispersion relation is directly measured, and a noise analysis is conducted. The obtained plasma, a mixture of shell and Maxwellian distributions, is found to emit waves within the Bernstein wave branches. By correlation measurements, a mode is found which is essentially an absolute instability in a narrow frequency band.

Urrutia, J. M.↗

Imaging the kinetics of anisotropic dissolution of bimetallic core–shell nanocubes using graphene liquid cells

Chemical design of multicomponent nanocrystals requires atomic-level understanding of reaction kinetics. Here, we apply single-particle imaging coupled with atomistic simulation to study reaction pathways and rates of Pd@Au and Cu@Au core-shell nanocubes undergoing oxidative dissolution. Quantitative analysis of etching kinetics using in situ transmission electron microscopy (TEM) imaging reveals that the dissolution mechanism changes from predominantly edge-selective to layer-by-layer removal of Au atoms as the reaction progresses. Dissolution of the Au shell slows down when both metals are exposed, which we attribute to galvanic corrosion protection. Morphological transformations are determined by intrinsic anisotropy due to coordination-number-dependent atom removal rates and extrinsic anisotropy induced by the graphene window. Our work demonstrates that bimetallic coreshell nanocrystals are excellent probes for the local physicochemical conditions inside TEM liquid cells. Furthermore, single-particle TEM imaging and atomistic simulation of reaction trajectories can inform future design strategies for compositionally and architecturally sophisticated nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Observation of Strong Two-Electron-One-Photon Transitions in Few-Electron Ions

We resonantly excite the K series of O5+ and O6+ up to principal quantum number n = 11 with monochromatic x rays, producing K-shell holes, and observe their relaxation by soft-x-ray emission. Some photoabsorption resonances of O5+ reveal strong two-electron–one-photon (TEOP) transitions. We find that for the [(1s2s)15p3/2]3/2;1/2 states, TEOP relaxation is by far stronger than the radiative decay and competes with the usually much faster Auger decay path. This enhanced TEOP decay arises from a strong correlation with the near-degenerate upper states [(1s2p3/2 )14s]3/2;1/2 of a Li-like satellite blend of the He-like Kα transition. Even in three-electron systems, TEOP transitions can play a dominant role, and the present results should guide further research on the ubiquitous and abundant many-electron ions where electronic energy degeneracies are far more common and configuration mixing is stronger.

M Togawa↗

Differentiating Between Simultaneous Loss Drivers in Earth's Outer Radiation Belt: Multi‐Dimensional Phase Space Density Analysis

Abstract We analyzed the contribution of electromagnetic ion cyclotron (EMIC) wave driven electron loss to a flux dropout event in September 2017. The evolution of electron phase space density (PSD) through the dropout showed the formation of a radially peaked PSD profile as electrons were lost at high L* , resembling distributions created by magnetopause shadowing. By comparing 2D Fokker Planck simulations of pitch angle diffusion to the observed change in PSD, we found that the μ and K of electron loss aligned with maximum scattering rates at dropout onset. We conclude that, during this dropout event, EMIC waves produced substantial electron loss. Because pitch angle diffusion occurred on closed drift paths near the last closed drift shell, no radial PSD minimum was observed. Therefore, the radial PSD gradients resembled solely magnetopause shadowing loss, even though the local pitch angle scattering produced electron losses of several orders of magnitude of the PSD.

Staples, F. A.↗

Quantifying electron temperature distributions from time-integrated x-ray emission spectra

K-shell x-ray emission spectroscopy is a standard tool used to diagnose the plasma conditions created in high-energy-density physics experiments. In the simplest approach, the emissivity-weighted average temperature of the plasma can be extracted by fitting an emission spectrum to a single temperature condition. It is known, however, that a range of plasma conditions can contribute to the measured spectra due to a combination of the evolution of the sample and spatial gradients. In this work, we define a parameterized model of the temperature distribution and use Markov Chain Monte Carlo sampling of the input parameters, yielding uncertainties in the fit parameters to assess the uniqueness of the inferred temperature distribution. Here we present the analysis of time-integrated S and Fe x-ray spectroscopic data from the Orion laser facility and demonstrate that while fitting each spectral region to a single temperature yields two different temperatures, both spectra can be fit simultaneously with a single temperature distribution. We find that fitting both spectral regions together requires a maximum temperature of $1310^{+90}_{-70}$ eV with significant contributions from temperatures down to 200 eV.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Oxide-Free Three-Dimensional Germanium/Silicon Core–Shell Metalattice Made by High-Pressure Confined Chemical Vapor Deposition

Metalattices are crystalline arrays of uniform particles in which the period of the crystal is close to some characteristic physical length scale of the material. In this work, we explore the synthesis and properties of a germanium metalattice in which the similar to 70 nm periodicity of a silica colloidal crystal template is close to the similar to 24 nm Bohr exciton radius of the nanocrystalline Ge replica. The problem of Ge surface oxidation can be significant when exploring quantum confinement effects or designing electronically coupled nanostructures because of the high surface area to volume ratio at the nanoscale. To eliminate surface oxidation, we developed a coreshell synthesis in which the Ge metalattice is protected by an oxide-free Si interfacial layer, and we explore its properties by transmission electron microscopy (TEM), Raman spectroscopy, and electron energy loss spectroscopy (EELS). The interstices of a colloidal crystal film grown from 69 nm diameter spherical silica particles were filled with polycrystalline Ge by high-pressure confined chemical vapor deposition (HPcCVD) from GeH4. After the SiO2 template was etched away with aqueous HF, the Ge replica was uniformly coated with an amorphous Si shell by HPcCVD as confirmed by TEM-EDS (energy-dispersive X-ray spectroscopy) and Raman spectroscopy. Formation of the shell prevents oxidation of the Ge core within the detection limit of XPS. The electronic properties of the core-shell structure were studied by accessing the Ge 3d edge onset using STEM-EELS. A blue shift in the edge onset with decreasing size of Ge sites in the metalattices suggests quantum confinement of the Ge core. The degree of quantum confinement of the Ge core depends on the void sizes in the template, which is tunable by using silica particles of varying size. The edge onset also shows a shift to higher energy near the shell in comparison with the Ge core. This shift along with the observation of Ge-Si vibrational modes in the Raman spectrum indicate interdiffusion of Ge and Si. Both the size of the voids in the template and core-shell interdiffusion of Si and Ge can in principle be tuned to modify the electronic properties of the Ge metalattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charging and ion ejection dynamics of large helium nanodroplets exposed to intense femtosecond soft xray pulses

Ion ejection from charged helium nanodroplets exposed to intense femtosecond soft X-ray pulses is studied by single-pulse ion time-of-flight (TOF) spectroscopy in coincidence with small-angle X-ray scattering. Scattering images encode the droplet size and absolute photon flux incident on each droplet, while ion TOF spectra are used to determine the maximum ion kinetic energy, Ekin, of He+ j fragments (j = 1-4). Measurements span HeN droplet sizes between N similar to 10(7) and similar to 10(10) (radii R-0 = 78-578 nm), and droplet charges between similar to 9x10(-5) and similar to 3x10(-3) e/atom. Conditions encompass a wide range of ionization and expansion regimes, from departure of all photoelectrons from the droplet, leading to pure Coulomb explosion, to substantial electron trapping by the electrostatic potential of the charged droplet, indicating the onset of hydrodynamic expansion. The unique combination of absolute Xray intensities, droplet sizes, and ion Ekin on an event-by-event basis reveals a detailed picture of the correlations between the ionization conditions and the ejection dynamics of the ionic fragments. The maximum E-kin of He+ is found to be governed by Coulomb repulsion from unscreened cations across all expansion regimes. The impact of ion-atom interactions resulting from the relatively low charge densities is increasingly relevant with less electron trapping. The findings are consistent with the emergence of a charged spherical shell around a quasineutral plasma core as the degree of ionization increases. The results demonstrate a complex relationship between measured ion E-kin and droplet ionization conditions that can only be disentangled through the use of coincident single-pulse TOF and scattering data.

Helium↗

Formation of tubular conduction channel in a SiGe(P)/Si core/shell nanowire heterostructure

Realizing a tubular conduction channel within a one-dimensional core–shell nanowire (NW) enables better understanding of quantum phenomena and exploration of electronic device applications. Herein, we report the growth of a SiGe(P)/Si core/shell NW heterostructure using a chemical vapor deposition coupled with vapor–liquid–solid growth mechanism. The entire NW heterostructure behaves as a p-type semiconductor, which demonstrates that the high-density carriers are confined within the 4 nm-thick Si shell and form a tubular conduction channel. These findings are confirmed by both calculations and the gate-dependent current–voltage ( I d – V g ) characteristics. Atomic resolution microscopic analyses suggest a coherent epitaxial core/shell interface where strain is released by forming dislocations along the axial direction of the NW heterostructure. Additional surface passivation achieved via growing a SiGe(P)/Si/SiGe core/multishell NW heterostructure suggests potential strategies to enhance the tubular carrier density, which could be further modified by improving multishell crystallinity and structural design.

36 MATERIALS SCIENCE↗

Discovery and characterization of an acridine radical photoreductant

Not provided.Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. Finally, we demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulation of multi-shell fullerenes using Machine-Learning Gaussian Approximation Potential

Multi-shell fullerenes ”buckyonions ” were simulated, starting from initially random configurations, using a density-functional-theory (DFT)-trained machine-learning carbon potential within the Gaussian Approximation Potential (GAP) Framework [Volker L. Deringer and Gábor Csányi, Phys. Rev. B 95, 094203 (2017)]. Fullerenes formed from seven different system sizes, ranging from 60 ~ 3774 atoms, were considered. The buckyonions are formed by clustering and layering starting from the outermost shell and proceeding inward. Inter-shell cohesion is partly due to interaction between delocalized π electrons protruding into the gallery. The energies of the models were validated ex post facto using density functional codes, VASP and SIESTA , revealing an energy difference within the range of 0.02 - 0.08 eV/atom after conjugate gradient energy convergence of the models was achieved with both methods.

74 ATOMIC AND MOLECULAR PHYSICS↗

Pionener 11 observations of effects of Ganymede and Callisto on Jupiter's trapped radiation

Charged particle data for low-energy protons and electrons from the Pioneer 11 high-latitude flyby of Jupiter in 1974 are reviewed in the light of the Voyager 1 magnetic field model of Connerney et al. (1981). It is found that if the trajectory of Pioneer 11 is mapped to the equatorial plane along the model magnetic field lines, significant features in the time-intensity profiles of trapped protons and electrons, including one microsignaturelike feature, are found to correspond to shells of closed field lines crossed by the orbits of Ganymede and Callisto. It is suggested that these features are signatures of interaction of the trapped particles with Ganymede and Callisto.

Mckibben, R. B.↗

A Plasma Instability Theory of GRB Emission

A new theory for gamma-ray burst radiation is presented. In this theory, magnetic fields and relativistic electrons are created through plasma processes arising as a relativistic shell passes through the interstellar medium. The gamma-rays are produced through synchrotron self-Compton emission. It is found that shocks do not arise in this theory, and that efficient gamma-ray emission only occurs for a high Lorentz factor and a high-density interstellar medium. The former explains the absence of gamma-ray bursts with thermal spectra. The latter provides the Compton attenuation theory with an explanation of why the interstellar medium density is always high. The theory predicts the existence of a class of extragalactic optical transient that emit no gamma-rays.

Brainerd, Jerome J.↗

The NSSDC trapped radiation model facility

The National Space Science Data Center (NSSDC) trapped radiation models calculate the integral and differential electron and proton flux for given values of the particle energy E, drift shell parameter L, and magnetic field strength B for either solar maximum or solar minimum. The most recent versions of the series of models, which have been developed and continuously improved over several decades by Dr. James Vette and coworkers at NSSDC, are AE-8 for electrons and AP-8 for protons. The present status of the NSSDC trapped particle models is discussed. The limits of validity of the models are described.

Gaffey, John D., Jr.↗

Size-Dependent Janus-Ligand Shell Formation on PbS Quantum Dots

We studied the size-dependent Janus ligand shell formation on PbS QDs employing an X-type ligand exchange reaction between native oleate ligands and two substituted cinnamic acid ligands, trifluoromethyl- and dimethyl amino-cinnamic acid, representing electron donating and electron withdrawing ligands. The exchange reactions become significantly more favorable for both electron donating and withdrawing ligands (..delta..G becomes more negative) in the smaller QDs compared to the larger QDs likely because the ligand density is smaller on the larger QDs reducing the strength of the ligand-ligand interactions. We found that Janus-ligand shells form more readily on smaller QDs than on bigger QDs with electron donating ligands. We also observed a dependence on the QD concentration that should be considered when forming Janus-ligand shells. Two-dimensional solution nuclear magnetic resonance spectroscopy (2D-NMR) shows evidence of pronounced phase segregation between oleate and electron donating ligands on the smaller QDs consistent with the enhanced ligand-ligand interactions. This study broadens our understanding of how to construct Janus and patchy ligand shell morphologies on small QDs.

14 SOLAR ENERGY↗

Conical-Domain Model for Estimating GPS Ionospheric Delays

The conical-domain model is a computational model, now undergoing development, for estimating ionospheric delays of Global Positioning System (GPS) signals. Relative to the standard ionospheric delay model described below, the conical-domain model offers improved accuracy. In the absence of selective availability, the ionosphere is the largest source of error for single-frequency users of GPS. Because ionospheric signal delays contribute to errors in GPS position and time measurements, satellite-based augmentation systems (SBASs) have been designed to estimate these delays and broadcast corrections. Several national and international SBASs are currently in various stages of development to enhance the integrity and accuracy of GPS measurements for airline navigation. In the Wide Area Augmentation System (WAAS) of the United States, slant ionospheric delay errors and confidence bounds are derived from estimates of vertical ionospheric delay modeled on a grid at regularly spaced intervals of latitude and longitude. The estimate of vertical delay at each ionospheric grid point (IGP) is calculated from a planar fit of neighboring slant delay measurements, projected to vertical using a standard, thin-shell model of the ionosphere. Interpolation on the WAAS grid enables estimation of the vertical delay at the ionospheric pierce point (IPP) corresponding to any arbitrary measurement of a user. (The IPP of a given user s measurement is the point where the GPS signal ray path intersects a reference ionospheric height.) The product of the interpolated value and the user s thin-shell obliquity factor provides an estimate of the user s ionospheric slant delay. Two types of error that restrict the accuracy of the thin-shell model are absent in the conical domain model: (1) error due to the implicit assumption that the electron density is independent of the azimuthal angle at the IPP and (2) error arising from the slant-to-vertical conversion. At low latitudes or at mid-latitudes under disturbed conditions, the accuracy of SBAS systems based upon the thin-shell model suffers due to the presence of complex ionospheric structure, high delay values, and large electron density gradients. Interpolation on the vertical delay grid serves as an additional source of delay error. The conical-domain model permits direct computation of the user s slant delay estimate without the intervening use of a vertical delay grid. The key is to restrict each fit of GPS measurements to a spatial domain encompassing signals from only one satellite. The conical domain model is so named because each fit involves a group of GPS receivers that all receive signals from the same GPS satellite (see figure); the receiver and satellite positions define a cone, the satellite position being the vertex. A user within a given cone evaluates the delay to the satellite directly, using (1) the IPP coordinates of the line of sight to the satellite and (2) broadcast fit parameters associated with the cone. The conical-domain model partly resembles the thin-shell model in that both models reduce an inherently four-dimensional problem to two dimensions. However, unlike the thin-shell model, the conical domain model does not involve any potentially erroneous simplifying assumptions about the structure of the ionosphere. In the conical domain model, the initially four-dimensional problem becomes truly two-dimensional in the sense that once a satellite location has been specified, any signal path emanating from a satellite can be identified by only two coordinates; for example, the IPP coordinates. As a consequence, a user s slant-delay estimate converges to the correct value in the limit that the receivers converge to the user s location (or, equivalently, in the limit that the measurement IPPs converge to the user s IPP).

Sparks, Lawrence↗