Similar Electron Densities Research Articles

Increased material differentiation through multi-contrast x-ray imaging: a preliminary evaluation of potential applications to the detection of threat materials

Most material discrimination in security inspections is based on dual-energy x-ray imaging, which enables the determination of a material’s effective atomic number (Zeff) as well as electron density and its consequent classification as organic or inorganic. Recently phase-based ‘dark-field’ x-ray imaging approaches have emerged that are sensitive to complementary features of a material, namely its unresolved microstructure. It can therefore be speculated that their inclusion in the security-based imaging could enhance material discrimination, for example of materials with similar electron densities and Zeff but different microstructures. In this paper, we present a preliminary evaluation of the advantages that such a combination could bear. Utilising an energy-resolved detector for a phase-based dark-field technique provides dual-energy attenuation and dark-field images simultaneously. In addition, since we use a method based on attenuating x-ray masks to generate the dark-field images, a fifth (attenuation) image at a much higher photon energy is obtained by exploiting the x-rays transmitted through the highly absorbing mask septa. In a first test, a threat material is imaged against a non-threat one, and we show how their discrimination based on maximising their relative contrast through linear combinations of two and five imaging channels leads to an improvement in the latter case. We then present a second example to show how the method can be extended to discrimination against more than one non-threat material, obtaining similar results. Albeit admittedly preliminary, these results indicate that significant margins of improvement in material discrimination are available by including additional x-ray contrasts in the scanning process.

Synthesis of linear and cyclic organic sulfonic acid-modified Cu-Al layered double hydroxides and their adsorption properties

Over the past few years, many substances have been investigated for their potential application as adsorbent materials. The combination of a layered double hydroxide (LDH) and CH/π interactions enables selective adsorption through the differences in the electron density of the aromatic ring. Thus, in this study, two organic anions, namely the linear 1-octane sulfonate (OS-) and cyclic sulfonated-β-cyclodextrin (SCD13-), were intercalated into the interlayers of a Cu-Al LDH by coprecipitation (Cu/Al ratio, 3.0; chemical ratio, 2.0). The SCD13- anion was selected because β-cyclodextrin comprises hydrophobic cavities that allow the formation of inclusion compounds. X-ray diffraction (XRD), total organic carbon (TOC) analysis, and inductively coupled plasma-atomic emission spectrometry (ICP-AES) revealed that the as-synthesized OS-Cu-Al LDH and SCD-Cu-Al LDH were both oriented perpendicular to the LDH layer. Subsequent absorption experiments with m-aminophenol (AP) and m-nitrophenol (NP), which have similar structures but different aromatic ring electron densities, confirmed a Freundlich-type adsorption mechanism and revealed that adsorption occurred on a non-uniform surface for both LDHs. The results also revealed excellent NP and AP adsorptions for the linear OS•Cu-Al LDH and cyclic SCD•Cu-Al LDH, respectively. This was attributed to the strong hydrophobic interactions in the former and strong CH/π interactions in the latter. This study shows the potential of using linear and cyclic organic sulfonic acid-modified LDHs for the selective recovery of the desired aromatic organic compounds.

Quantitative analysis of the evolution of ASR products and crack networks in the context of the concrete mesostructure

Methodological challenges have long been an obstacle for the understanding of damage in concrete due to the alkali-silica reaction (ASR). Time-lapse X-ray tomography could be key to advancements but has not been extensively exploited, mainly due to similar electron densities of the different material phases, which leads to poor contrast in the tomograms. To address this limitation, we propose the implementation of two complementary contrast agents, BaSO4 and CsNO3. After optimizing the contents of both agents synergistically for mortars, we realize for the first time a quantitative characterization of the spatial-temporal distributions of both ASR products and cracks, while differentiating their presence in aggregates and in cement paste. This new methodology allowed showing that similar amounts of ASR products were found inside the aggregates and inside the cement paste. The transport of products from inner aggregate regions into the cement paste along propagating cracks was followed in 4D.

Effect of Ligand Structure on the Electron Density and Activity of Iridium Catalysts for the Borylation of Alkanes.

An in-depth study of iridium catalysts for the borylation of alkyl C-H bonds is reported. Although the borylation of aryl C-H bonds can be catalyzed by iridium complexes containing phen or bpy ligands at mild temperatures and with limiting arene, the borylation of alkyl C-H bonds remains underdeveloped. We prepared a library of phenanthrolines that contain varying substitution patterns. The corresponding phen-Ir trisboryl carbon monoxide complexes were synthesized to determine the electron-donating ability of these ligands, and the initial rates for the borylation of the C-H bonds in THF and diethoxyethane β to oxygen catalyzed by Ir complexes containing these ligands were measured. For some subsets of these ligands, the donor ability correlated positively with the rate of C-H borylation catalyzed by the complexes containing ligands within a given subset. However, across subsets, ligands possessing similar donor properties to one another form catalysts for the borylation of alkyl C-H bonds with widely varying activity. This phenomenon was investigated computationally, and it was discovered that the stabilizing interactions between the phenanthroline ligand and the boryl ligands attached to Ir in the transition state for C-H oxidative addition could account for the differences in the activity of the catalysts that possess similar electron densities at Ir. The effect of these interactions on the borylation of secondary alkyl C-H bonds is larger than it is on the borylation of primary alkyl C-H bonds.

Extraction Performance of a Fluorous Phosphate for Zr(IV) from HNO3 Solution: Comparison with Tri-n-Butyl Phosphate

ABSTRACTWe compare the extraction performance of new extractant, fluorous phosphate tris(4,4,5,5,6,6,7,7,7-nonafluoroheptyl) phosphate (TFP) in the fluorinated diluent perfluorohexane, for Zr(IV) with a conventional organic extractant, tri-n-butyl phosphate (TBP) in n-octane. It is surprising that fluorinating TBP to TFP improved the extraction performance, as normally fluorinating the hydrocarbon substituents on neutral extractants tends to decrease the extraction strength. We examined the origin of the superior extraction performance of TFP by analyzing the equilibrium of the chemical reaction during the extraction. The equilibrium reaction of Zr(IV) with TFP is , whereas that with TBP is . Phosphorus-31 nuclear magnetic resonance and infrared spectroscopy measurements of TFP and TBP showed similar electron densities at the phosphorus atom and vibration modes of the P=O group, implying similar coordination to Zr(IV). In addition, the concentrations of all components (Zr(IV), HNO3, and water) in the fluorous and organic phases after solvent extraction were evaluated by inductively coupled plasma-mass spectrometry, ion chromatography, and Karl-Fischer titration. The concentrations of water and HNO3 molecules in the fluorous phase become low during the Zr(NO3)4(TFP)3 extraction, indicating that water and HNO3 molecules do not preferentially interact with Zr(NO3)4(TFP)3 in contrast to Zr(NO3)4(TBP)2 in n-octane We speculate that the excellent performance originated from the stability of Zr(NO3)4(TFP)3 in the fluorous phase. Hence, TFP is expected to be used as an alternative extractant to TBP.

Larger sized planar wire arrays of complex configuration on 1.5–1.8 MA Z-pinch generator

Two new approaches of (i) simultaneous study of implosion and radiative characteristics of different materials in wire array Z-pinch plasmas in one shot and (ii) investigation of larger sized wire arrays (to enhance energy coupling to plasmas and provide better diagnostic access) were developed in experiments with 1.5–1.8 MA Zebra with a Load Current Multiplier. In particular, the larger sized multi-plane Planar Wire Arrays with two outer planes placed at 9 and 15 mm from each other and then as far as at 19 mm (compared with 6 mm studied before at standard 1 MA current) and with a modified central plane with 8 to 12 empty slots were investigated. Though K-shell Al and L-shell Ni, Cu plasmas have similar electron temperatures and densities, the ablation dynamics and radiation of Al and Ni, Cu planes are somewhat different, which was investigated in detail using the full set of diagnostics and modeling. Advantages of using such wire arrays at higher currents to study plasma flow and radiation from different materials and jets are highlighted.

Supersonic jets of hydrogen and helium for laser wakefield acceleration

The properties of laser wakefield accelerated electrons in supersonic gas flows of hydrogen and helium are investigated. At identical backing pressure, we find that electron beams emerging from helium show large variations in their spectral and spatial distributions, whereas electron beams accelerated in hydrogen plasmas show a higher degree of reproducibility. In an experimental investigation of the relation between neutral gas density and backing pressure, it is found that the resulting number density for helium is ∼30% higher than for hydrogen at the same backing pressure. The observed differences in electron beam properties between the two gases can thus be explained by differences in plasma electron density. This interpretation is verified by repeating the laser wakefield acceleration experiment using similar plasma electron densities for the two gases, which then yielded electron beams with similar properties.

Modulation doping of GaAs/AlGaAs core-shell nanowires with effective defect passivation and high electron mobility.

Reliable doping is required to realize many devices based on semiconductor nanowires. Group III-V nanowires show great promise as elements of high-speed optoelectronic devices, but for such applications it is important that the electron mobility is not compromised by the inclusion of dopants. Here we show that GaAs nanowires can be n-type doped with negligible loss of electron mobility. Molecular beam epitaxy was used to fabricate modulation-doped GaAs nanowires with Al0.33Ga0.67As shells that contained a layer of Si dopants. We identify the presence of the doped layer from a high-angle annular dark field scanning electron microscopy cross-section image. The doping density, carrier mobility, and charge carrier lifetimes of these n-type nanowires and nominally undoped reference samples were determined using the noncontact method of optical pump terahertz probe spectroscopy. An n-type extrinsic carrier concentration of 1.10 ± 0.06 × 10(16) cm(-3) was extracted, demonstrating the effectiveness of modulation doping in GaAs nanowires. The room-temperature electron mobility was also found to be high at 2200 ± 300 cm(2) V(-1) s(-1) and importantly minimal degradation was observed compared with undoped reference nanowires at similar electron densities. In addition, modulation doping significantly enhanced the room-temperature photoconductivity and photoluminescence lifetimes to 3.9 ± 0.3 and 2.4 ± 0.1 ns respectively, revealing that modulation doping can passivate interfacial trap states.

Face-Capping μ3-BO in B6(BO)7–: Boron Oxide Analogue of B6H7– with Rhombic 4c–2e Bonds

Using the first-principle approaches, we predict a B6(BO)7(-) cluster with a face-capping μ(3)-BO, which is the boron oxide analogue of closo-B6H7(-) with a face-capping μ(3)-H. Detailed topological analysis of electron density clearly reveals the existence of three rhombic 4c-2e bonds around the B/H apex in both C3v B6(BO)7(-) and C3v B6H7(-), which possesses similar electron densities at their bond and ring critical points. The adaptive natural density partitioning (AdNDP) analysis provides a direct and visual picture of the B-B-B-B/H 4c-2e bonds for the first time. Adiabatic and vertical electron detachment energies of the concerned monoanions are calculated to facilitate their future photoelectron spectroscopy measurements and characterizations. The presence of the B6(BO)7(-) and B6H7(-) clusters extends the BO/H isolobal analogy to the whole μ(n)-BO/H series (n = 1, 2, and 3) and enriches the chemistry of boronyl.

Modeling electron density distributions from X-ray diffraction to derive optical properties: Constrained wavefunction versus multipole refinement

The rational design of next-generation optical materials requires an understanding of the connection between molecular structure and the solid-state optical properties of a material. A fundamental challenge is to utilize the accurate structural information provided by X-ray diffraction to explain the properties of a crystal. For years, the multipole refinement has been the workhorse technique for transforming high-resolution X-ray diffraction datasets into the detailed electron density distribution of crystalline material. However, the electron density alone is not sufficient for a reliable calculation of the nonlinear optical properties of a material. Recently, the X-ray constrained wavefunction refinement has emerged as a viable alternative to the multipole refinement, offering several potential advantages, including the calculation of a wide range of physical properties and seeding the refinement process with a physically reasonable starting point. In this study, we apply both the multipole refinement and the X-ray constrained wavefunction technique to four molecules with promising nonlinear optical properties and diverse structural motifs. In general, both techniques obtain comparable figures of merit and generate largely similar electron densities, demonstrating the wide applicability of the X-ray constrained wavefunction method. However, there are some systematic differences between the electron densities generated by each technique. Importantly, we find that the electron density generated using the X-ray constrained wavefunction method is dependent on the exact location of the nuclei. The X-ray constrained wavefunction refinement makes smaller changes to the wavefunction when coordinates from the Hartree-Fock-based Hirshfeld atom refinement are employed rather than coordinates from the multipole refinement, suggesting that coordinates from the Hirshfeld atom refinement allow the X-ray constrained wavefunction method to produce more accurate wavefunctions. We then use the experimentally derived wavefunctions to calculate the molecular dipole moment, polarizability, hyperpolarizability, and refractive index and show that these are in good agreement with the values calculated using ab initio methods. Thus, this study shows that experimental wavefunctions can be reliably generated from X-ray diffraction datasets, and that optical properties can be reliably calculated from these wavefunctions. Such a concerted interplay of experiment and computation via the X-ray constrained wavefunction refinement stands to enable the molecular engineering of tailor-made next-generation optical materials.

Highly electron deficient pyrido[3′,2′:4,5]furo[2,3-b]pyridine as a core structure of a triplet host material for high efficiency green phosphorescent organic light-emitting diodes

Highly electron deficient pyrido[3',2':4,5]furo[2,3-b]pyridine (PFP) was developed as a core structure of a triplet host material and a derivative of PFP, 3-(3-(carbazole-9-yl)phenyl) pyrido[3',2':4,5]furo[2,3-b]pyridine (CzPFP), was synthesized as a bipolar host material. The CzPFP host material showed similar hole and electron densities in single charge devices, and a high quantum efficiency of 27.7% and a high power efficiency of 86.8 lm W(-1) in green phosphorescent organic light-emitting diodes.

Anharmonic atomic vibrations in the relaxor ferroelectric Pb(Mg1/3Nb2/3)O3under pressure

Structural analyses of the relaxor ferroelectric material Pb(Mg${}_{1/3}$Nb${}_{2/3}$)O${}_{3}$ (PMN) with single-crystal x-ray diffraction under pressure in a diamond anvil cell indicate static atomic displacement and chemical disorder. A difference Fourier analysis within the framework of a harmonic oscillator model for the atomic vibrations reveals residual electron density on both the Pb and Nb(Mg) sites. Pb atoms in the $A$ site of the $AB$O${}_{3}$ perovskite structure exhibit a greater displacement than the Nb(Mg) atoms in the $B$ site, despite the fact that Pb is a much heavier atom. The displacement is interpreted in terms of an anharmonic statistical atomic motion. At pressures above 2.5 GPa the displacement disappears, consistent with previous observations. The difference Fourier maps reveal no residual electron densities greater than 1 $e$/\AA{}${}^{3}$ at any atomic position, and these appear to be induced by the violation of local electrical neutrality arising from both Mg${}^{2+}$ and Nb${}^{5+}$ ions located at the octahedral site. Similar electron densities are observed at all experimental pressures and in refinements based on both harmonic and anharmonic models. The anharmonic parameters taken into account are the higher-order tensors of atomic elastic motion. At high pressure, where the relaxor transforms to a paraelectric phase, the residual electron densities disappear.

Camelback channel for fast decay of LO phonons in GaN heterostructure field-effect transistor at high electron density

Fluctuation technique is used to measure hot-phonon lifetime in dual channel GaN-based configuration proposed to support high-power operation at high frequencies. The channel is formed of a composite Al0.1Ga0.9N/GaN structure situated in an Al0.82In0.18N/AlN/Al0.1Ga0.9N/GaN heterostructure. According to capacitance–voltage measurements and simultaneous treatment of Schrödinger–Poisson equations, the mobile electrons in this dual channel configuration form a camelback density profile at elevated hot-electron temperatures. The hot-phonon lifetime was found to depend on the shape of the electron profile rather than solely on its sheet density. The camelback channel with an electron sheet density of 1.8 × 1013 cm−2 demonstrates ultrafast decay of hot phonons at hot-electron temperatures above 600 K: the hot-phonon lifetime is below ∼60 fs in contrast to ∼600 fs at an electron sheet density of 1.2 × 1013 cm−2 obtained in a reference Al0.82In0.18N/AlN/GaN structure at 600 K. The results suggest a suitable method to increase the electron sheet density without the deleterious effect caused by inefficient hot-phonon decay observed in a standard design at similar electron densities.

Influence of atomic species on laser pulse propagation in underdense plasmas

Abstract A 65 fs, intense ( ∼ 10 18 Wcm − 2 ) laser pulse incident on a supersonic, laminar gas-jet was investigated via 90° Thomson Scattering and interferometry diagnostics. In order to study the effect of atomic species on laser pulse propagation, the laser interaction with different gases (Nitrogen and Argon) was monitored. In the experimental conditions, both the atomic species resulted in similar electron densities, however, early diffraction of the laser pulse was observed in Argon gas, while, stable propagation of the pulse over several Rayleigh lengths was seen in the case of Nitrogen gas target. Features of the scattering region indicate a competition between optical diffraction and intensity dependent non-linear focusing of the pulse. The observations suggest that proper choice of the target is essential within the available laser pulse parameters, as it can enhance or spoil the propagation of laser pulse in plasmas.

Scaling Laws of Solar and Stellar Flares

In this study we compile for the first time comprehensive data sets of solar and stellar flare parameters, including flare peak temperatures Tp, flare peak volume emission measures EMp, and flare durations τf from both solar and stellar data, as well as flare length scales L from solar data. Key results are that both the solar and stellar data are consistent with a common scaling law of EMp ∝ T4.7p, but the stellar flares exhibit ≈250 times higher emission measures (at the same flare peak temperature). For solar flares we observe also systematic trends for the flare length scale L(Tp) ∝ T0.9p and the flare duration τF(Tp) ∝ T0.9p as a function of the flare peak temperature. Using the theoretical RTV scaling law and the fractal volume scaling observed for solar flares, i.e., V(L) ∝ L2.4, we predict a scaling law of EMp ∝ T4.3p, which is consistent with observations, and a scaling law for electron densities in flare loops, np ∝ T2p/L ∝ T1.1p. The RTV-predicted electron densities were also found to be consistent with densities inferred from total emission measures, np = (EMp/qVV)1/2, using volume filling factors of qV = 0.03–0.08 constrained by fractal dimensions measured in solar flares. Solar and stellar flares are expected to have similar electron densities for equal flare peak temperatures Tp, but the higher emission measures of detected stellar flares most likely represent a selection bias of larger flare volumes and higher volume filling factors, due to low detector sensitivity at higher temperatures. Our results affect also the determination of radiative and conductive cooling times, thermal energies, and frequency distributions of solar and stellar flare energies.

Effect of MBE Growth Conditions on Multiple Electron Transport in InN

A quantitative mobility spectrum analysis (QMSA) of multiple magnetic field data has been used to determine the transport properties of bulk and surface electron species in InN films, grown by plasma-assisted molecular beam epitaxy (PAMBE) with varying substrate temperatures and In/N flux ratios. While all films have similar bulk electron densities, ∼4 × 1017 cm−3, the highest mobility was obtained in the highest growth temperature film (3100 cm2/V s at 150 K), while In-rich growth also gave good mobility values even at a much lower growth temperature. The surface sheet electron concentration increased with surface roughness, which increased with N-flux during growth.

Laser light backscatter from intermediate and high Z plasmas

In experiments at the Omega Laser Facility [J. M. Soures et al., Fusion Technol. 30, 492 (1996)], stimulated Brillouin backscatter (SBS) from gasbags filled with krypton and xenon gases was ten times lower than from CO2-filled gasbags with similar electron densities. The SBS backscatter was a 1%–5% for both 527 and 351nm interaction beams at an intensity of ∼1015W∕cm2. The SRS backscatter was less than 1%. The 351nm interaction beam is below the threshold for filamentation and the SBS occurs in the density plateau between the blast waves. Inverse bremsstrahlung absorption of the incident and SBS light account for the lower reflectivity from krypton than from CO2. The 527nm interaction beam filaments in the blowoff plasma before the beam propagates through the blast wave, where it is strongly absorbed. Thus, most of the 527nm SBS occurs in the flowing plasma outside the blast waves.

Spin-dependent electron transport through a magnetic resonant tunneling diode

Electron transport properties in nanostructures can be modeled, for example, by using the semiclassical Wigner formalism or the quantum mechanical Green's functions formalism. We compare the performance and the results of these methods in the case of magnetic resonant-tunneling diodes. We have implemented the two methods within the self-consistent spin-density-functional theory. Our numerical implementation of the Wigner formalism is based on the finite-difference scheme whereas for the Green's function formalism the finite-element method is used. As a specific application, we consider the device studied by Slobodskyy et all. [Phys. Rev. Lett. 90, 246601 (2003)] and analyze their experimental results. The Wigner and Green's functions formalisms give similar electron densities and potentials but, surprisingly, the former method requires much more computer resources in order to obtain numerically accurate results for currents. Both of the formalisms can successfully be used to model magnetic resonant tunneling diode structures.

Comparison of deuterium and hydrogen experiments in the Sustained Spheromak Physics Experiment

In this paper we report on the results of deuterium and hydrogen experiments in the Sustained Spheromak Physics Experiment (SSPX). We have compared ∼500 deuterium discharges with similar discharges in hydrogen. Typically, we produce H2 plasmas with peak toroidal currents in the range of 0.6MA, electron temperatures (Te) of ∼200eV and energy confinement times (τE) of ∼200μs. The D2 fueled discharges show similar results to those with H2 fueling with no obvious differences in confinement time. Electron temperatures of ∼200 eV with similar electron densities were observed. Both the deuterium and hydrogen fueled discharges have a calculated thermal diffusivity below χe<10m2/s. However, the D2 fueled discharges had a factor of ∼5 increase in high-Z (titanium) impurity content suggesting an increase of physical sputtering. We find no significant mass scaling effects.

Growth of tin-doped indium antimonide for magnetoresistors

Magnetoresistors made from n-type indium antimonide are of interest for magnetic position sensing applications. In this study, tin-doped indium antimonide was grown by the metalorganic chemical vapor deposition technique using trimethylindium, trisdimethylaminoantimony, and tetraethyltin in a hydrogen ambient. Using a growth temperature of 370°C and a pressure of 200 Torr, it was found that the electron density in tin-doped films varied from 3.3×1016 cm−3 to 4.0×1017 cm−3 as the 5/3 ratio was varied from 4.8 to 6.8. From secondary ion mass spectroscopy (SIMS) studies, it was found that this variation is not caused by a change in site occupancy of the tin atoms from antimony to indium lattice sites, but rather to a change in the total tin concentration incorporated into the films. This dependence of tin incorporation on stoichiometry could be used to rapidly vary the doping level during growth. Undoped films grown under similar conditions had electron densities of about 2×1016 cm−3 and electron mobilities near 50,000 cm2V−1s−1 at room temperature for films that were only 1.5 µm thick on a gallium arsenide substrate. Attempts to grow indium antimonide at 280°C resulted in p-type material caused by carbon incorporation. The carbon concentration as measured with SIMS increased rapidly with increasing growth rate, to above 1019 cm−3 at 0.25 µm/h. This is apparently caused by incomplete pyrolysis of a reactant at this low growth temperature. Growth at 420°C resulted in rough surface morphologies. Finally, it was demonstrated that films with excellent electron mobility and an optimized doping profile for magnetoresistors can be grown.