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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 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Tuning the electronic structure of SrTiO{sub 3}/SrFeO{sub 3−x} superlattices via composition and vacancy control

Using density functional theory-based calculations, we explore the effects of oxygen vacancies and epitaxial layering on the atomic, magnetic, and electronic structure of (SrTiO{sub 3}){sub n}(SrFeO{sub 3−x}){sub 1} superlattices. While structures without oxygen vacancies (x = 0) possess small or non-existent band gaps and ferromagnetic ordering in their iron layers, those with large vacancy concentrations (x = 0.5) have much larger gaps and antiferromagnetic ordering. Though the computed gaps depend numerically on the delicate energetic balance of vacancy ordering and on the value of Hubbard U{sub eff} used in the calculations, we demonstrate that changes in layering can tune the band gaps of these superlattices below that of SrTiO{sub 3} (3.2 eV) by raising their valence band maxima. This suggests the possibility that these superlattices could absorb in the solar spectrum, and could serve as water-splitting photocatalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Photoelectron velocity-map imaging and theoretical studies of heteronuclear metal carbonyls MNi(CO){sub 3}{sup −} (M = Mg, Ca, Al)

The heteronuclear metal carbonyl anions MNi(CO){sub 3}{sup −} (M = Mg, Ca, Al) have been investigated using photoelectron velocity-map imaging spectroscopy. Electron affinities of neutral MNi(CO){sub 3} (M = Mg, Ca, Al) are measured from the photoelectron spectra to be 1.064 ± 0.063, 1.050 ± 0.064, and 1.541 ± 0.040 eV, respectively. The C–O stretching mode in these three clusters is observed and the vibrational frequency is determined to be 2049, 2000, and 2041 cm{sup −1} for MgNi(CO){sub 3}, CaNi(CO){sub 3}, and AlNi(CO){sub 3}, respectively. Density functional theory calculations are carried out to elucidate the geometric and electronic structures and to aid the experimental assignments. It has been found that three terminal carbonyls are preferentially bonded to the nickel atom in these heterobinuclear nickel carbonyls MNi(CO){sub 3}{sup −1/0}, resulting in the formation of the Ni(CO){sub 3} motif. Ni remains the 18-electron configuration for MgNi(CO){sub 3} and CaNi(CO){sub 3} neutrals, but not for AlNi(CO){sub 3}. This is different from the homobinuclear nickel carbonyl Ni–Ni(CO){sub 3} with the involvement of three bridging ligands. Present findings would be helpful for understanding CO adsorption on alloy surfaces.

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

Magnetic properties of Fe-Mn-Pt for heat assisted magnetic recording applications

We calculate the electronic structures of FePt and Fe{sub 0.5}Mn{sub 0.5}Pt using first-principles calculations based on density functional theory within the local-spin-density approximation. The Curie temperature (T{sub c}) was calculated by mean field approximation. Composition dependence of the Cure temperature (T{sub c}(x)) of Fe{sub 1−x}Mn{sub x}Pt was used to identify a composition to meet the desired T{sub c} in the range of 600–650 K. The identified composition (0.0294 ≤ x ≤ 0.0713) gives saturation magnetization (M{sub s}) in the range of 1041–919 emu/cm{sup 3} and magnetocrystalline anisotropy constant (K) in the range of 9.96–8.36 × 10{sup 6 }J/m{sup 3} at 0 K. Temperature dependent M(T) and K(T) of Fe{sub 1−x}Mn{sub x}Pt (0.0294 ≤ x ≤ 0.0713) were calculated using the Brillouin function and Callen-Callen experimental relation, respectively. Fe{sub 1−x}Mn{sub x}Pt (0.0294 ≤ x ≤ 0.0713) shows 930–800 emu/cm{sup 3} of M{sub s} and 7.18–5.61 × 10{sup 6 }J/m{sup 3} of K at 300 K, thereby satisfying desired magnetic properties for heat-assisted magnetic recording media to achieve 4 Tb/in.{sup 2} areal density.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Magnetic Properties and Electronic Structure of Co/Zr Multilayers

We investigate the magnetic and electronic properties of Co/Zr multilayers with an emphasis on the interfacial effects. The saturation magnetization, coercivity, and uniaxial anisotropy depend significantly on Co thickness. Spin-wave resonance modes were observed, and the change of resonant field as a function of mode number (n) obeys the so-called n{sup 2} law. The interlayer coupling constant was determined. The electronic properties of the interfacial alloys were studied using the WIEN2k code, employing the density functional theory. Calculations describe satisfactorily the observed magnetic behaviour. The influence of pressure on the magnetic properties of the interfacial Co{sub 1−x}Zr{sub x} alloys was investigated in which we demonstrate that the ferromagnetism is altered by pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Slow photoelectron velocity-map imaging spectroscopy of the Fe{sub 3}O{sup –} and Co{sub 3}O{sup –} anions

We report high-resolution photoelectron spectra of the transition metal suboxide clusters Fe{sub 3}O{sup −} and Co{sub 3}O{sup −}{sub .} The combination of slow electron velocity-map imaging and cryogenic cooling yields vibrationally well-resolved spectra, from which we obtain precise values of 1.4408(3) and 1.3951(4) eV for the electron affinities of Fe{sub 3}O and Co{sub 3}O. Several vibrational frequencies of the neutral ground state Fe{sub 3}O and Co{sub 3}O clusters are assigned for the first time, and a low-lying excited state of Fe{sub 3}O is observed. The experimental results are compared with density functional electronic structure calculations and Franck-Condon spectral simulations, enabling identification of the structural isomer and electronic states. As has been found in photoelectron spectra of other trimetal oxo species, Fe{sub 3}O{sup 0/−} and Co{sub 3}O{sup 0/−} are assigned to a μ{sub 2}-oxo isomer with planar C{sub 2v} symmetry. We identify the ground states of Fe{sub 3}O{sup –} and Co{sub 3}O{sup –} as {sup 12}A{sub 1} and {sup 9}B{sub 2} states, respectively. From these states we observe photodetachment to the {sup 11}B{sub 2} ground and {sup 13}A{sub 1} excited states of Fe{sub 3}O, as well as to the {sup 8}A{sub 1} ground state of Co{sub 3}O.

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

Characterization of one-dimensional molecular chains of 4,4′-biphenyl diisocyanide on Au(111) by scanning tunneling microscopy

The morphology and electronic structure of vapor deposited 4,4′-biphenyldiisocyanide (BPDI) on a Au(111) surface were investigated using variable-temperature scanning tunneling microscopy. When deposited at room temperature, BPDI molecules form one-dimensional molecular chains similar to that recently observed for the structurally related 1,4-phenyl diisocyanide (PDI). Compared to PDI, the longer periodicity for the BPDI molecular chains is consistent with the addition of a second phenyl ring and supports a structural model in which the BPDI molecules lie parallel to the surface and interconnected by Au-adatoms. The molecular chains are mostly aligned along the [11{sup -}0] direction of the Au(111) substrate, but exhibit frequent changes in angle that are consistent with directions between fcc and hcp three-fold hollow sites. Dispersion-corrected density functional theory calculations for one-dimensional chains of BPDI molecules bound end-to-end via their isocyanide groups to Au-adatoms reproduce the observed periodicity of the chains and show that this morphology is energetically favored over upright binding with one free —NC group. The spatially resolved conductance (dI/dV) map for BPDI on Au(111) exhibits a feature centered at −0.67 eV below the Fermi level which are delocalized along the chain with maxima at the Au-adatom and biphenyl positions. This occupied resonant feature is close to that previously observed for the PDI in both photoemission and conductance measurements and is attributed to an occupied interfacial state resulting from BPDI-Au interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Modeling intrinsic defects in LiNbO{sub 3} within the Slater-Janak transition state model

Intrinsic point defects in LiNbO{sub 3}, i.e., isolated Nb antisites and Li as well Nb vacancies, are investigated from first-principles within the Slater-Janak transition state model. Thereby the electronic structure of the investigated defects is calculated with hybrid exchange-correlation functionals. This approach allows for the calculation of charge transition levels without comparing the total energies of differently charged supercells. The obtained results are in agreement with previous hybrid density-functional theory calculations based on total-energy differences. Li and Nb vacancies can be formed in the V{sub Li}{sup −} and V{sub Nb}{sup 5−} charge states only, as long as the host is not strongly p-type or n-type, respectively. Nb{sub Li} antisites may capture one or two electrons, forming the defect states often referred to as small bound polaron and bi-polaron.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Understanding the Kondo resonance in the d-CoPc/Au(111) adsorption system

By combining the density functional theory (DFT) and a hierarchical equations of motion (HEOM) approach, we investigate the Kondo phenomena in a composite system consisting of a dehydrogenated cobalt phthalocyanine molecule (d-CoPc) adsorbed on an Au(111) surface. DFT calculations are performed to determine the ground-state geometric and electronic structures of the adsorption system. It is found that the singly occupied d{sub z{sup 2}} orbital of Co forms a localized spin, which could be screened by the substrate conduction electrons. This screening leads to the prominent Kondo features as observed in the scanning tunneling microscopy experiments. We then employ the HEOM approach to characterize the Kondo correlations of the adsorption system. The calculated temperature-dependent differential conductance spectra and the predicted Kondo temperature agree well with the experiments, and the universal Kondo scaling behavior is correctly reproduced. This work thus provides important insights into the relevant experiments, and it also highlights the applicability of the combined DFT+HEOM approach to the studies of strongly correlated condensed matter systems.

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

Potential energy surfaces for high-energy N + O 2 collisions

Potential energy surfaces for high-energy collisions between an oxygen molecule and a nitrogen atom are useful for modeling chemical dynamics in shock waves. In the present work, we present doublet, quartet, and sextet potential energy surfaces that are suitable for studying collisions of O 2 ( 3 Σ$^{–}_{g}$) with N( 4 S) in the electronically adiabatic approximation. Two sets of surfaces are developed, one using neural networks (NNs) with permutationally invariant polynomials (PIPs) and one with the least-squares many-body (MB) method, where a two-body part is an accurate diatomic potential and the three-body part is expressed with connected PIPs in mixed-exponential-Gaussian bond order variables (MEGs). We find, using the same dataset for both fits, that the fitting performance of the PIP-NN method is significantly better than that of the MB-PIP-MEG method, even though the MB-PIP-MEG fit uses a higher-order PIP than those used in previous MB-PIP-MEG fits of related systems (such as N 4 and N 2 O 2 ). However, the evaluation of the PIP-NN fit in trajectory calculations requires about 5 times more computer time than is required for the MB-PIP-MEG fit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Electronic structures and magnetic performance related to spintronics of Sr{sub 0.875}Ti{sub 0.125}S

In this study, we have used the first-principle approaches of density functional theory to determine the electronic and magnetic performances related to spintronics applications of titanium (Ti)-substituted SrS such as Sr{sub 1−x}Ti{sub x}S at concentration x = 0.125. The results of electronic and magnetic properties by using TB–mBJ potential revealed that Sr{sub 0.875}Ti{sub 0.125}S compound is half-metallic ferromagnetic with a half-metallic gap and a spin polarization of 100%. The ferromagnetic nature of Sr{sub 0.875}Ti{sub 0.125}S material is confirmed by the ferromagnetic coupling between magnetic moments of Ti, Sr and S atoms. The total magnetic moment of integer Bohr magneton of 2 μ{sub B} and the large half-metallic gap of 1.245 suggest that this compound is a true half-metallic ferromagnet.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Structure and electronic properties of a Mn nanowire encapsulated in carbon nanotubes

First-principles calculations using density functional theory are performed studying the stability and the electronic structure of an one-dimensional chain of Mn atoms as a nanowire encapsulated in a single-walled (5,5) armchair carbon nanotube. The results show a ferromagnetic ground state for a dimerized nanowire where the interatomic Mn–Mn distance is 2.65 Å and the interdimer separation is 3.40 Å. The average Mn moment is 4.35μ B . A charge transfer from the nanotube to the nanowire is observed. A polarized spin channel is identified for conduction electrons in the filled nanotube. - Graphical abstract: Spin density for a Mn nanowire encapsulated in a carbon nanotube. Highlights: • A Mn nanowire can be stabilized in a single-walled armchair carbon nanotube. • The ground state is ferromagnetic. • The average moment on the Mn atoms is 4.35μ B . • A polarized spin channel is identified for conduction electrons in the filled nanotube.

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

Hybrid functional band gap calculation of SnO{sub 6} containing perovskites and their derived structures

We have studied the properties of SnO{sub 6} octahedra-containing perovskites and their derived structures using ab initio calculations with different density functionals. In order to predict the correct band gap of the materials, we have used B3LYP hybrid density functional, and the results of B3LYP were compared with those obtained using the local density approximation and generalized gradient approximation data. The calculations have been conducted for the orthorhombic ground state of the SnO{sub 6} containing perovskites. We also have expended the hybrid density functional calculation to the ASnO{sub 3}/A'SnO{sub 3} system with different cation orderings. We propose an empirical relationship between the tolerance factor and the band gap of SnO{sub 6} containing oxide materials based on first principles calculation. - Graphical abstract: (a) Structure of ASnO{sub 3} for orthorhombic ground state. The green ball is A (Ba, Sr, Ca) cation and the small (red) ball on edge is oxygen. SnO{sub 6} octahedrons are plotted as polyhedron. (b) Band gap of ASnO{sub 3} as a function of the tolerance factor for different density functionals. The experimental values of the band gap are marked as green pentagons. (c) ASnO{sub 3}/A'SnO{sub 3} superlattices with two types cation arrangement: [001] layered structure and [111] rocksalt structure, respectively. (d) B3LYP hybrid functional band gaps of ASnO{sub 3}, [001] ordered superlattices, and [111] ordered superlattices of ASnO{sub 3}/A'SnO{sub 3} as a function of the effective tolerance factor. Note the empirical linear relationship between the band gap and effective tolerance factor. - Highlights: • We report the hybrid functional band gap calculation of ASnO{sub 3} and ASnO{sub 3}/A'SnO{sub 3}. • The band gap of ASnO{sub 3} using B3LYP functional reproduces the experimental value. • We propose the linear relationship between the tolerance factor and the band gap.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Enhanced efficiency of p-type doping by band-offset effect in wurtzite and zinc-blende GaAs/InAs-core-shell nanowires

Using first principles calculation based on density-functional theory, we investigated p-type electronic structures and the doping mechanism in wurtzite (WZ) and zinc-blende (ZB) GaAs/InAs-core-shell nanowires (NWs) along the [0001] and [111] directions, respectively. Comparing the doping in WZ and ZB core-shell NWs, we found it is easier and more stable to realize dopant in WZ NWs. Due to the type I band-offset, p-type doping in the GaAs-core of GaAs{sub core}/InAs{sub shell} for both WZ and ZB NWs makes that the valence band-edge electrons in the InAs-shell can spontaneously transfer to the impurity states, forming one-dimensional hole gas. In particular, this process accompanies with a reverse transition in WZ core-shell nanowire due to the existence of antibonding and bonding states.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Electronic structure changes during the surface-assisted formation of a graphene nanoribbon

High conductivity and a tunability of the band gap make quasi-one-dimensional graphene nanoribbons (GNRs) highly interesting materials for the use in field effect transistors. Especially bottom-up fabricated GNRs possess well-defined edges which is important for the electronic structure and accordingly the band gap. In this study we investigate the formation of a sub-nanometer wide armchair GNR generated on a Au(111) surface. The on-surface synthesis is thermally activated and involves an intermediate non-aromatic polymer in which the molecular precursor forms polyanthrylene chains. Employing angle-resolved two-photon photoemission in combination with density functional theory calculations we find that the polymer exhibits two dispersing states which we attribute to the valence and the conduction band, respectively. While the band gap of the non-aromatic polymer obtained in this way is relatively large, namely 5.25 ± 0.06 eV, the gap of the corresponding aromatic GNR is strongly reduced which we attribute to the different degree of electron delocalization in the two systems.

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

Adsorption of a metalorganic complex at a metal surface: A density functional theory study vs. model description

A modification of the electronic and magnetic structure of a metalorganic complex by chemisorption at a metallic surface is addressed. The density functional theory (DFT) is applied to investigate a simplified form of a copper-dioxolene complex in a free state and connected to Au(111) surface with alkanethiol linkers. A systematic study of the dependence of the system electronic structure on the linker length is performed. It is found that the electronic structure of the complex is well preserved during the adsorption process. The magnetic moment of the Cu-dioxolene functional group is shown to be strictly correlated with the amount of the charge residing at the complex. On the basis of the DFT results, a model Hamiltonian of the adsorbed metalorganic system is proposed. The model is an extension of the Sandorfy's model of the alkanes and includes explicitly Coulomb interaction between electrons both within the alkane's backbone and the end group. We show that the latter feature is necessary to understand the evolution of the system's properties with the length of the linkers. The advantage of this approach is that it not only reproduces the main results of our DFT analysis but also provides a simple common basis to analyse a wide class of metal complexes bound to metal surfaces with alkanethiol linkers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Band structure engineering of anatase TiO{sub 2} by metal-assisted P-O coupling

In this work, we demonstrate that the metal-assisted P-O coupling is an effective approach to improve the photoelectrochemical properties of TiO{sub 2}. The (Sc + P) and (In + P) codoping effects on electronic structures and photocatalytic activities of anatase TiO{sub 2} are examined by performing hybrid density functional theory calculations. It is found that the coupling of P dopant with the second-nearest neighboring O atom assisted by acceptor metals (Sc/In) leads to the fully occupied and delocalized intermediate bands within the band gap of anatase TiO{sub 2}, which is driven by the P-O antibonding states (π*). This metal-assisted P-O coupling can prevent the recombination of photogenerated electron-hole pairs and effectively reduce the band gap of TiO{sub 2}. Moreover, the band edge alignments in (Sc + P) and (In + P) codoped anatase TiO{sub 2} are desirable for water-splitting. The calculated optical absorption curves indicate that (Sc + P) and (In + P) codoping in anatase TiO{sub 2} can also effectively enhance the visible light absorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework

We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capability by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO{sub 2}(110)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗