Properties of Inconel 625 mesh structures grown by electron beam additive manufacturing
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List, F. A.↗
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Results for “electronics”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Electronic and Molecular Structures of the CeB 6 Monomer
The electronic and molecular structure of the CeB 6 molecular unit has been probed by anion PE spectroscopy and DFT calculations to gain insight into structural and electronic relaxation on edge and corner sites of this ionic material. While boron in bulk lanthanide hexaboride materials assumes octahedral B 6 3– units, the monomer assumes a less compact structure to delocalize the charge. Two competitive molecular structures were identified for the anion and neutral species, which include a boat-like structure and a planar or near-planar teardrop structure. Ce adopts different orbital occupancies in the two isomers; the boat-like structure has a 4f superconfiguration while the teardrop favors a 4f 6s occupancy. The B 6 ligand in these structures carries a charge of –4 and –3, respectively. The teardrop structure, which was calculated to be isoenergetic with the boat structure, was most consistent with the experimental spectrum. B 6 -local orbitals crowd the energy window between the Ce 4f and 6s (HOMO) orbitals. A low-lying transition from the B-based orbitals is observed slightly less than 1 eV above the ground state. Here, the results suggest that edge and corner conductivity involves stabilized, highly diffuse 6s orbitals or bands rather than the bulk-favored 5d band. High-spin and open-shell low-spin states were calculated to be very close in energy for both the anion and neutral, a characteristic that reflects how decoupled the 4f electron is from the B 6 2p- and Ce 6s-based molecular orbitals.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Reorganization Energies for Interfacial Proton-Coupled Electron Transfer to a Water Oxidation Catalyst
The reorganization energy (λ) for interfacial electron transfer (ET) and proton-coupled electron transfer (PCET) from a conductive metal oxide (In 2 O 3 :Sn, ITO) to a surface-bound water oxidation catalyst were extracted from kinetic data measured as a function of the thermodynamic driving force. Visible light excitation resulted in rapid excited-state injection (k inj > 10 8 s -1 ) to the ITO, which photo-initiated the two interfacial reactions of interest. The rate constants for both reactions increased with the driving force, −ΔG°, to a saturating limit, k max , with rate constants consistently larger for ET than for PCET. Marcus-Gerischer analysis of the kinetic data provided the reorganization energy for interfacial PCET (0.90 ± 0.02 eV) and ET (0.40 ± 0.02 eV), respectively. The magnitude of k max for PCET was found to decrease with pH, behavior that was absent for ET. Both the decrease in k max and the larger reorganization energy for an unwanted competing PCET reaction from the ITO to the oxidized catalyst showcases a significant kinetic advantage for driving solar water oxidation at high pH. Computational analysis revealed a larger inner-sphere reorganization energy contribution for PCET than for ET arising from a more significant change in the Ru–O bond length for PCET. Extending Marcus-Gerischer theory to PCET by including the excited electron-proton vibronic states and the proton donor-acceptor motion provided an apparent reorganization energy of 1.01 eV. Furthermore, this study demonstrates that the Marcus-Gerischer theory initially developed for ET can be reliably extended to PCET for quantifying and interpreting reorganization energies observed experimentally.
Catalysts Kinetic parameters↗
General Kinetic Model for pH Dependence of Proton-Coupled Electron Transfer: Application to an Electrochemical Water Oxidation System
The pH dependence of proton-coupled electron transfer (PCET) reactions, which are critical to many chemical and biological processes, is a powerful probe for elucidating their fundamental mechanisms. Herein, a general, multichannel kinetic model is introduced to describe the pH dependence of both homogeneous and electrochemical PCET reactions. According to this model, a weak pH dependence can arise from the competition among multiple sequential and concerted PCET channels involving different forms of the redox species, such as protonated and deprotonated forms, as well as different proton donors and acceptors. The contribution of each channel is influenced by the relative populations of the reactant species, which often depend strongly on pH, leading to complex pH dependence of PCET apparent rate constants. This model is used to explain the origins of the experimentally observed weak pH dependence of the electrochemical PCET apparent rate constant for a ruthenium-based water oxidation catalyst attached to a tin-doped In2O3 (ITO) surface. The weak pH dependence is found to arise from the intrinsic differences in the rate constants of participating channels and the dependence of their relative contributions on pH. This model predicts that the apparent maximum rate constant will become pH-independent at higher pH, which is confirmed by experimental measurements. Our analysis also suggests that the dominant channels are electron transfer at lower pH and sequential PCET via electron transfer followed by fast proton transfer at higher pH. Furthermore, this work highlights the importance of considering multiple competing channels simultaneously for PCET processes.
Catalysts↗
Giant onsite electronic entropy enhances the performance of ceria for water splitting
Abstract not provided
30 DIRECT ENERGY CONVERSION↗
Discovery and construction of surface kagome electronic states induced by p-d electronic hybridization in Co3Sn2S2
Abstract Kagome-lattice materials possess attractive properties for quantum computing applications, but their synthesis remains challenging. Herein, based on the compelling identification of the two cleavable surfaces of Co 3 Sn 2 S 2 , we show surface kagome electronic states (SKESs) on a Sn-terminated triangular Co 3 Sn 2 S 2 surface. Such SKESs are imprinted by vertical p-d electronic hybridization between the surface Sn (subsurface S) atoms and the buried Co kagome-lattice network in the Co 3 Sn layer under the surface. Owing to the subsequent lateral hybridization of the Sn and S atoms in a corner-sharing manner, the kagome symmetry and topological electronic properties of the Co 3 Sn layer is proximate to the Sn surface. The SKESs and both hybridizations were verified via qPlus non-contact atomic force microscopy (nc-AFM) and density functional theory calculations. The construction of SKESs with tunable properties can be achieved by the atomic substitution of surface Sn (subsurface S) with other group III-V elements (Se or Te), which was demonstrated theoretically. This work exhibits the powerful capacity of nc-AFM in characterizing localized topological states and reveals the strategy for synthesis of large-area transition-metal-based kagome-lattice materials using conventional surface deposition techniques.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Electronic origin of reorganization energy in interfacial electron transfer
Electron transfer (ET) reactions underpin energy conversion and chemical transformations in both biological and a biological systems. The efficiency of any ET process relies on achieving a desired ET rate within an optimal driving force range. Marcus theory provides a microscopic framework for understanding the activation free energy—and therefore the rate—of ET in terms of a key parameter: the reorganization energy. For electrified solid–liquid interfaces, it has long been conventionally understood that only factors in the electrolyte phase are responsible for determining the reorganization energy and that the electronic density of states (DOS) of the electrode only serves to dictate the number of thermally accessible channels for ET. Here we show instead that the electrode DOS plays a central role in governing the reorganization energy, far outweighing its conventionally assumed role. Using atomically layered heterostructures, we tune the DOS of graphene and measure outer-sphere ET kinetics. We find the ensuing variation in ET rate arises from strong modulation in a reorganization energy associated with image potential localization in the electrode. Here we redefine the traditional paradigm of heterogeneous ET kinetics, revealing a deeper role of the electrode electronic structure in interfacial reactivity.
Electrochemistry↗
Electronic structure and electron-phonon coupling in TiH$_2$
Calculations using first principles methods and strong coupling theory are carried out to understand the electronic structure and superconductivity in cubic and tetragonal TiH$_2$. A large electronic density of states at the Fermi level in the cubic phase arises from Ti-$t_{2g}$ states and leads to a structural instability against tetragonal distortion at low temperatures. However, constraining the in-plane lattice constants diminishes the energy gain associated with the tetragonal distortion, allowing the cubic phase to be stable at low temperatures. Furthermore, calculated phonon dispersions show decoupled acoustic and optic modes arising from Ti and H vibrations, respectively and frequencies of optic modes to be rather high. The cubic phase has a large electron-phonon coupling parameter $\lambda$ and critical temperature of several K. Contribution of the hydrogen sublattice to $\lambda$ is found to be small in this material, which we understand from strong coupling theory to be due to the small H-$s$ DOS at the Fermi level and high energy of hydrogen modes at the tetrahedral sites.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Dependence of synergy current driven by lower hybrid wave and electron cyclotron wave on the frequency and parallel refractive index of electron cyclotron wave for Tokamaks
The physical mechanism of the synergy current driven by lower hybrid wave (LHW) and electron cyclotron wave (ECW) in tokamaks is investigated using theoretical analysis and simulation methods in the present paper. Research shows that the synergy relationship between the two waves in velocity space strongly depends on the frequency ω and parallel refractive index N{sub //} of ECW. For a given spectrum of LHW, the parameter range of ECW, in which the synergy current exists, can be predicted by theoretical analysis, and these results are consistent with the simulation results. It is shown that the synergy effect is mainly caused by the electrons accelerated by both ECW and LHW, and the acceleration of these electrons requires that there is overlap of the resonance regions of the two waves in velocity space.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Density fitting for three-electron integrals in explicitly correlated electronic structure theory
The principal challenge in using explicitly correlated wavefunctions for molecules is the evaluation of nonfactorizable integrals over the coordinates of three or more electrons. Immense progress was made in tackling this problem through the introduction of a single-particle resolution of the identity. Decompositions of sufficient accuracy can be achieved, but only with large auxiliary basis sets. Density fitting is an alternative integral approximation scheme, which has proven to be very reliable for two-electron integrals. Here, we extend density fitting to the treatment of all three-electron integrals that appear at the MP2-F12/3*A level of theory. We demonstrate that the convergence of energies with respect to auxiliary basis size is much more rapid with density fitting than with the traditional resolution-of-the-identity approach.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Oblique propagation of ion acoustic soliton-cnoidal waves in a magnetized electron-positron-ion plasma with superthermal electrons
The oblique propagation of ion-acoustic soliton-cnoidal waves in a magnetized electron-positron-ion plasma with superthermal electrons is studied. Linear dispersion relations of the fast and slow ion-acoustic modes are discussed under the weak and strong magnetic field situations. By means of the reductive perturbation approach, Korteweg-de Vries equations governing ion-acoustic waves of fast and slow modes are derived, respectively. Explicit interacting soliton-cnoidal wave solutions are obtained by the generalized truncated Painlevé expansion. It is found that every peak of a cnoidal wave elastically interacts with a usual soliton except for some phase shifts. The influence of the electron superthermality, positron concentration, and magnetic field obliqueness on the soliton-cnoidal wave are investigated in detail.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Tailoring of polarization in electron blocking layer for electron confinement and hole injection in ultraviolet light-emitting diodes
The influence of the AlGaN electron blocking layer (EBL) with graded aluminum composition on electron confinement and hole injection in AlGaN-based ultraviolet light-emitting diodes (LEDs) are investigated. The light output power of LED with graded AlGaN EBL was markedly improved, comparing to LED with conventional EBL. In experimental results, a high increment of 86.7% can be obtained in light output power. Simulation analysis shows that via proper modification of the barrier profile from the last barrier of the active region to EBL, not only the elimination of electron overflow to p-type layer can be achieved but also the hole injection into the active region can be enhanced, compared to a conventional LED structure. The dominant factor to the performance improvement is shown to be the modulation of polarization field by the graded Al composition in EBL.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Magnetic collimation of relativistic positrons and electrons from high intensity laser–matter interactions
Collimation of positrons produced by laser-solid interactions has been observed using an externally applied axial magnetic field. The collimation leads to a narrow divergence positron beam, with an equivalent full width at half maximum beam divergence angle of 4° vs the un-collimated divergence of about 20°. A fraction of the laser-produced relativistic electrons with energies close to those of the positrons is collimated, so the charge imbalance ratio (n{sub e−}/n{sub e+}) in the co-propagating collimated electron-positron jet is reduced from ∼100 (no collimation) to ∼2.5 (with collimation). The positron density in the collimated beam increased from 5 × 10{sup 7} cm{sup −3} to 1.9 × 10{sup 9} cm{sup −3}, measured at the 0.6 m from the source. This is a significant step towards the grand challenge of making a charge neutral electron-positron pair plasma jet in the laboratory.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Theoretical study of thorium monoxide for the electron electric dipole moment search: Electronic properties of H{sup 3}Δ{sub 1} in ThO
Recently, improved limits on the electron electric dipole moment, and dimensionless constant, k{sub T,P}, characterizing the strength of the T,P-odd pseudoscalar–scalar electron–nucleus neutral current interaction in the H{sup 3}Δ{sub 1} state of ThO molecule were obtained by the ACME collaboration [J. Baron et al., Science 343, 269 (2014)]. The interpretation of the experiment in terms of these fundamental quantities is based on the results of theoretical study of appropriate ThO characteristics, the effective electric field acting on electron, E{sub eff}, and a parameter of the T,P-odd pseudoscalar–scalar interaction, W{sub T,P}, given in Skripnikov et al. [J. Chem. Phys. 139, 221103 (2013)] by St. Petersburg group. To reduce the uncertainties of the given limits, we report improved calculations of the molecular state–specific quantities E{sub eff}, 81.5 GV/cm, and W{sub T,P}, 112 kHz, with the uncertainty within 7% of the magnitudes. Thus, the values recommended to use for the upper limits of the quantities are 75.8 GV/cm and 104 kHz, correspondingly. The hyperfine structure constant, molecule-frame dipole moment of the H{sup 3}Δ{sub 1} state, and the H{sup 3}Δ{sub 1} → X{sup 1}Σ{sup +} transition energy which, in general, can serve as a measure of reliability of the obtained E{sub eff} and W{sub T,P} values are also calculated. In addition, we report the first calculation of g-factor for the H{sup 3}Δ{sub 1} state of ThO. The results are compared to the earlier experimental and theoretical studies, and a detailed analysis of uncertainties of the calculations is given.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Electronic structure and optical properties of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} solid-solution thin films
We have examined the effect of V doping on the electronic and optical properties of epitaxial hematite (α-Fe{sub 2}O{sub 3}) thin films, by employing several characterization techniques and computational modeling. The conductivity of α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} (0 ≤ x ≤ ∼0.5) is enhanced by several orders of magnitude as x is increased, as evidenced by electrical resistivity measurements and x-ray photoelectron spectroscopy core-level and valence-band spectra. Optical absorption shows a reduction in the direct band gap by as much as 0.64 eV for x = 0.53 (E{sub g} = 1.46 eV) relative to that of α-Fe{sub 2}O{sub 3} (E{sub g} = 2.10 eV). Detailed understanding of the character of the optical transitions in the alloys is achieved using first-principles calculations of the ground and excited states. These calculations reveal that V doping results in occupied V 3d orbitals hybridized with Fe orbitals and located at approximately mid-gap in α-Fe{sub 2}O{sub 3}. The lowest energy transitions involve charge transfer from occupied V 3d to unoccupied Fe 3d* orbitals. With a low band gap and high conductivity, α-(Fe{sub 1-x}V{sub x}){sub 2}O{sub 3} is a promising material for photovoltaic and photoelectrochemical applications.
36 MATERIALS SCIENCE↗
Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV
The electronic state spectroscopy of carbonyl sulphide, COS, has been investigated using high resolution vacuum ultraviolet photoabsorption spectroscopy and electron energy loss spectroscopy in the energy range of 4.0–10.8 eV. The spectrum reveals several new features not previously reported in the literature. Vibronic structure has been observed, notably in the low energy absorption dipole forbidden band assigned to the (4π←3π) ({sup 1}Δ←{sup 1}Σ{sup +}) transition, with a new weak transition assigned to ({sup 1}Σ{sup −}←{sup 1}Σ{sup +}) reported here for the first time. The absolute optical oscillator strengths are determined for ground state to {sup 1}Σ{sup +} and {sup 1}Π transitions. Based on our recent measurements of differential cross sections for the optically allowed ({sup 1}Σ{sup +} and {sup 1}Π) transitions of COS by electron impact, the optical oscillator strength f{sub 0} value and integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis. Subsequently, ICSs predicted by the scaling are confirmed down to 60 eV in the intermediate energy region. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of carbonyl sulphide in the upper stratosphere (20–50 km)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗