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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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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Manipulating the Geometric and Electronic Structures of Manganese Nitrides for Ammonia Synthesis

Abstract Manganese (Mn) nitrides are important nitrogen (N) carriers for small‐scale intermittent ammonia (NH 3 ) synthesis. However, only 3∼8 % of lattice N are converted into NH 3 . In this study, the geometric and electronic structures of well‐defined Mn 4 N and Mn 2 N lattices were altered using transition metal heteroatoms (Cr, Fe, Co, Ni, Mo) to understand the driving force behind lattice N diffusion and extraction. Density Functional Theory (DFT) revealed that the binding of early hydrogenation product (NH) follows a linear relationship with lattice N over a wide range of close‐packed surfaces. But, the binding of NH 2 and NH 3 are more sensitive to the geometric and electronic structures. Further, the chemical bonding can be quantitatively characterized with the covalency derived from Crystal Orbital Hamiltonian Population (COHP). In the Eley Rideal‐Mars van Krevelan pathway, the overall NH 3 formation free energy ( ) and lattice N diffusion barrier ( ) are the respective thermodynamic and kinetic determining factors. Aided by a rate‐determining step (RDS) model, Mn 4 N modified with Fe, Co, Ni single‐atom dopants all show enhanced rates for NH 3 formation.

Shan, Nannan↗
DOE OSTI2011

Hydrogen-anion formation near a (2x1)-reconstructed Si(100) surface: Substrate-electronic-structure and trajectory dependence

We calculated the yield of outgoing hydrogen negative ions after the reflection of 1-keV neutral hydrogen atoms from a (2x1)-reconstructed Si(100) surface. We find that the charge-transfer dynamics at the reconstructed surface is dependent on both the surface-electronic structure and orientation of the projectile trajectory relative to the crystal azimuthal directions. Our results are in good quantitative agreement with the measured H{sup -} fractions of Maazouz and Esaulov [Surf. Sci. 398, 49 (1998)] for scattering trajectories that are aligned perpendicularly to rows of silicon dimers.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Electronic structure and aromaticity of large-scale hexagonal graphene nanoflakes

With the help of the recently developed SIESTA-pole (Spanish Initiative for Electronic Simulations with Thousands of Atoms) - PEXSI (pole expansion and selected inversion) method [L. Lin, A. García, G. Huhs, and C. Yang, J. Phys.: Condens. Matter 26, 305503 (2014)], we perform Kohn-Sham density functional theory calculations to study the stability and electronic structure of hydrogen passivated hexagonal graphene nanoflakes (GNFs) with up to 11 700 atoms. We find the electronic properties of GNFs, including their cohesive energy, edge formation energy, highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap, edge states, and aromaticity, depend sensitively on the type of edges (armchair graphene nanoflakes (ACGNFs) and zigzag graphene nanoflakes (ZZGNFs)), size and the number of electrons. We observe that, due to the edge-induced strain effect in ACGNFs, large-scale ACGNFs’ edge formation energy decreases as their size increases. This trend does not hold for ZZGNFs due to the presence of many edge states in ZZGNFs. We find that the energy gaps E{sub g} of GNFs all decay with respect to 1/L, where L is the size of the GNF, in a linear fashion. But as their size increases, ZZGNFs exhibit more localized edge states. We believe the presence of these states makes their gap decrease more rapidly. In particular, when L is larger than 6.40 nm, we find that ZZGNFs exhibit metallic characteristics. Furthermore, we find that the aromatic structures of GNFs appear to depend only on whether the system has 4N or 4N + 2 electrons, where N is an integer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structural, electronic, superconducting and mechanical properties of ReC and TcC

The structural, electronic, superconducting and mechanical properties of ReC and TcC are investigated using density functional theory calculations. The lattice constants, bulk modulus, and the density of states are obtained. The calculated lattice parameters are in good agreement with the available results. The density of states reveals that ReC and TcC exhibit metallic behavior at ambient condition. A pressure-induced structural phase transition is observed in both materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Experimental electronic structures of the Fe IV =O bond in S=1 heme vs. nonheme sites: Effect of the porphyrin ligand

High-valent Fe IV =O species are common intermediates in biological and artificial catalysts. Heme and nonheme S=1 Fe IV =O sites have been synthesized and studied for decades but little quantitative experimental comparison of their electronic structures has been available, due to the lack of direct methods focused on the iron. This study allows a rigorous determination of the electronic structure of a nonheme Fe IV =O center and its comparison to an Fe IV =O heme site using 1s2p resonant inelastic X-ray scattering (RIXS) and Fe L-edge X-ray absorption spectroscopy (XAS). Further, variable temperature magnetic circular dichroism (VT-MCD) of the ligand field transitions, combined with nuclear resonance vibrational spectroscopy of the two S=1 Fe IV =O systems show that the equatorial ligand field decreases from a nonheme to a heme Fe IV =O site. Alternatively, RIXS and Fe L-edge XAS combined with MCD show that the Fe dπ orbitals are unperturbed in the Fe IV =O heme relative to the nonheme site because the strong axial Fe-O bond uncouples the Fe dπ orbitals from the porphyrin π-system. As a consequence, the thermodynamics and kinetics of the H-atom abstraction reactions are actually very similar for heme compound II and nonheme Fe IV =O active sites.

bioinorganic chemistry↗
DOE OSTI2018

Electronic Structure of OR-AgInS{sub 2} and TiO{sub 2} Crystals and Its Differential Characteristics

The electronic structures of orthorhombic silver–indium sulfide and rutile titanium oxide were calculated within the framework of density functional theory using the basis of numerical pseudoatomic orbitals in the LDA and GGA approximations. The features of their electron energy spectra and the character of chemical bonds were considered. The comparative analysis of obtained bandgap widths and effective masses determined for heavy electrons and holes in the Brillouin zone center on the basis of analytical derivatives of one-electron energies was performed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes

Here, a series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C 5 Me 5 ) 2 Th(Cl)[P(Mes) 2 ] (Mes = mesityl = 2,4,6-(CH 3 ) 3 C 6 H 2 ; dark red-purple), (C 5 Me 5 ) 2 Th[P(Mes)(CH 3 )] 2 (dark red-purple), (C 5 Me 5 ) 2 Th(CH 3 )[P(Mes) 2 ] (dark red-purple), (C 5 Me 5 ) 2 Th(CH 3 )[P(Mes)(SiMe 3 )] (orange), (C 5 Me 5 ) 2 Th(Cl)[P(Mes)(SiMe 3 )] (orange), (C 5 Me 5 ) 2 Th[P(Mes)(SiMe 3 )] 2 (orange), and (C 5 Me 5 ) 2 Th[PH(Mes)] 2 (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using 31 P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electronic structure of van der Waals ferromagnet CrI 3 from self-consistent vertex corrected GW approaches

Electronic structure of the layered van der Waals ferromagnet CrI 3 is studied with self consistent diagrammatic approaches beyond the GW approximation. Considerable improvement in the calculated band gap as compared to the non-self-consistent G0W0 results has been found. Certain spectral features in the valence bands discovered recently by the angle resolved photoemission spectroscopy, are reproduced better when we use full frequency dependent self energy. Density functional theory and the quasiparticle self-consistent GW method which are based on the frequency-independent self energy are unable to resolve these features. The non-locality effects in the diagrams beyond the GW approximation are large for both polarizability and self energy. This finding can potentially have an impact on the development of methods like the GW+DMFT (dynamical mean field theory).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2012

Distribution of cations in wurtzitic In x Ga 1-x N and In x Al 1-x N alloys: Consequences for energetics and quasiparticle electronic structures

The ternary, isostructural, wurtzite-derived group-III mononitride alloys In x Ga 1-x N andIn x Al 1-x N are reexamined within a cluster expansion approach. Using density functional theory together with the AM05 exchange-correlation functional, the total energies and the optimized atomic geometries of all 22 clusters classes of the cluster expansion for each material system are calculated. The computationally demanding calculation of the corresponding quasiparticle electronic structures is achieved for all cluster classes by means of a recently developed scheme to approximately solve the quasiparticle equation based on the HSE06 hybrid functional and the G₀W₀ approach. Using two different alloy statistics, the configurational averages for the lattice parameters, the mixing enthalpies, and the bulk moduli are calculated. The composition-dependent electronic structures of the alloys are discussed based on configurationally averaged electronic states, band gaps, and densities of states. Ordered cluster arrangements are found to be energetically rather unfavorable, however, they possess the smallest energy gaps and, hence, contribute to light emission. The influence of the alloy statistics on the composition dependencies and the corresponding bowing parameters of the band gaps is found to be significant and should, hence, lead to different signatures in the optical-absorption or -emission spectra.

de Carvalho, Luiz Cláudio↗
DOE OSTI2024

Electronic structure and magnetic and transport properties of antiferromagnetic Weyl semimetal GdAlSi

Here we report the topological electronic structure, magnetic, and magnetotransport properties of a noncentrosymmetric compound GdAlSi. Magnetic susceptibility shows an antiferromagnetic transition at TN = 32 K. In-plane isothermal magnetization exhibits an unusual hysteresis behavior at higher magnetic field, rather than near zero field. Moreover, the hysteresis behavior is asymmetric under positive and negative magnetic fields. First-principles calculations were performed on various magnetic configurations, revealing that the antiferromagnetic state is the ground state, and the spiral antiferromagnetic state is a close competing state. The calculations also reveal that GdAlSi hosts multiple Weyl points near the Fermi energy. The band structure measured by angle-resolved photoemission spectroscopy (ARPES) shows relatively good agreement with the theory, with the possibility of Weyl nodes slightly above the Fermi energy. Within the magnetic ordered state, we observe an exceptionally large anomalous Hall conductivity (AHC) of ~ 1310 Ω-1cm-1 at 2 K. Interestingly, the anomalous Hall effect persists up to room temperature with a significant value of AHC (~ 155 Ω-1cm-1). Our analysis indicates that the large AHC originates from the Berry curvature associated with the multiple pairs of Weyl points near Fermi energy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2011

The morphology, electron structure, and optical properties of self-assembled silicon nanostructures on the surface of highly oriented pyrolytic graphite

The results of studies of the morphology, electronic structure, and optical properties of self-assembled silicon nanostructures on the surface of highly oriented pyrolytic graphite are reported. The structures are fabricated by electron-beam-assisted evaporation in high-vacuum conditions. It is found that, at thicknesses of about one monolayer, the atomic structure of the layer is similar to that of graphene with the interatomic spacing {approx}2.4 A. At film thicknesses larger than one monolayer, clusters about 5 nm in dimensions are formed on the substrate surface.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Revealing the electronic structure of the current-induced metastable state in 1T-TaS 2

Among the key features for next-generation memory devices is the need for high-contrast switching between metallic and insulating states with fast switching speed and long lifetime. However, materials exhibiting such properties are rare, and their electronic structure is often poorly understood. Here, by combining state-of-the-art devices with angle-resolved photoemission spectroscopy, we study the emergence of a metastable metallic state from the insulating ground state in the charge-density wave (CDW) material 1T-TaS 2 after applying short current pulses. Analysis of the electronic structure suggests a picture in which 1T-TaS 2 transforms from a band insulator in the commensurate CDW ground state to a correlated metal in the metastable state. Moreover, the optically induced metastable state reveals a strong similarity to the current-induced one. This work provides an extensive characterization of metastable order in 1T-TaS 2 and proves how studying electronic properties under in-operando conditions is a critical step for next-generation devices.

Huber, Maximilian [Lawrence Berkeley National Labo↗
DOE OSTI2018

Changes in Electronic Structure upon Li Deintercalation from LiCoPO 4 Derivatives

On the path toward the design of Li-ion batteries with increased energy densities, efforts are focused on the development of positive electrodes that can maximize the voltage of the full cell. However, the development of novel materials that operate at high voltage, while also showing high efficiency and meeting strict safety standards, is an ongoing challenge. LiCoPO 4 is being explored as a possible candidate, as the Co 2+/3+ redox couple operates at 4.8 V versus Li + /Li 0 . The presence of phosphate groups is typically expected to stabilize the compound against oxygen loss, yet the changes in Co-O bonding upon Li extraction have not been ascertained. In addition, LiCoPO 4 is riddled with problems relating to poor transport and strain in the crystal structure of the delithiated phase, which handicap its use as a high-voltage electrode. In this work, substituting ions to generate Li 1.025 Co 0.84 Fe 0.10 Cr 0.05 Si 0.01 (PO 4 ) 1.025 is found to stabilize both the electronic structure and crystal structure and, therefore, substantially improve the ability to fully utilize the redox capacity of the material. A thorough study by spectroscopic tools, combined with computations of the electronic structure, was used to probe changes in chemical bonding. The measurements revealed the existence of redox gradients between surface and bulk that are common in other materials that react at high potential. Lastly, the study offers a comprehensive understanding of the fundamental reactions in LiCoPO 4 -type frameworks, while further demonstrating that ion substitution is an effective tool for improving their performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Stability, electronic structures and transport properties of armchair (10, 10) BN/C nanotubes

Using the first-principle calculations, the stability and electronic properties of two novel types of four-segment armchair (10, 10) BN/C hybrid nanotubes ((BN){sub 5}C{sub 5}(BN){sub 5}C{sub 5}NT and (BN){sub 5}C{sub 5}(NB){sub 5}C{sub 5}NT) as well as two-segment armchair (10, 10) BN/C hybrid nanotubes ((BN{sub 20−n}C{sub n}NTs) are systematically investigated. When n increases from 1 to 4, the band gap of (BN){sub 20−n}C{sub n}NTs gradually decreases to a narrow one. When 4≤n≤17, the electronic structure of carbon segment in (BN){sub 20−n}C{sub n}NTs behaves as zigzag graphene nanoribbons whose band gap is modulated by an inherent electric field of the BN segment. ZGNR-like segments in (BN){sub 5}C{sub 5}(BN){sub 5}C{sub 5}NT and (BN){sub 5}C{sub 5}(NB){sub 5}C{sub 5}NT behave as narrow gap semiconductor and metal, respectively, due to their different chemical environment. Moreover, the (BN){sub 5}C{sub 5}(NB){sub 5}C{sub 5}NT can separate electron and hole carriers, indicating its potential application in solar cell materials. Obvious transport enhancement around the Fermi level is found in the four-segment nanotubes, especially a 6G{sub 0} transmission peak in the metallic (BN){sub 5}C{sub 5}(NB){sub 5}C{sub 5}NT. - Graphical abstract: Structural diagram of four-segment (BN){sub 5}C{sub 5}(NB){sub 5}C{sub 5}NT and its typical two-probe system. The band structures and transport spectra of (BN){sub 5}C{sub 5}(NB){sub 5}C{sub 5}NT are shown in upper and lower panels. Highlights: ► Transport properties of two types of four-segment BNC hybrid nanotubes are studied. ► Transport enhancements are realized in the four-segment BNC hybrid nanotubes. ► Electron and hole separation is found in four-segment BNC hybrid nanotubes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Electronic structure of ion arsenic high temperature superconductors studied by angle resolved photoemission spectroscopy

The main purpose of the present thesis is to present our ARPES results on the iron arsenic superconductors. As revealed by a series of ARPES measurements on both the AEFe2As2 and the RFeAs(O,F) families (parent compound and carrier-doped systems), the electronic structures of the pnictides are complicated, three dimensional, and closely linked to their superconducting behavior (13; 14; 15; 16; 17; 18; 19). Parent compounds of these materials exhibit the basic hole-electron pocket dual plus an apparent Fermi surface reconstruction caused by long range antiferromagnetism (13; 15). When carriers are introduced, the chemical potential shifts in accordance with the Luttinger theorem and the rigid band shifting picture (13). Importantly, both the appearance and disappearance of the superconducting dome at low and high doping levels have intimate relation with topological changes at the Fermi surfaces, resulting in a specific Fermi topology being favored by superconductivity (15; 16). On the low doping side, superconductivity emerges in the phase diagram once the antiferromagnetic reconstruction disappears below the Fermi level, returning the Fermi surface to its paramagnetic-like appearance. On the high doping side, superconductivity disappears around a doping level at which the central hole pocket vanishes due to increasing electron concentration. Such phenomena are evidence for the governing role the electronic structure plays in their superconducting behavior.

36 MATERIALS SCIENCE↗