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At least 1,729 records · Page 96
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DOE OSTI2014

First principles electronic band structure and phonon dispersion curves for zinc blend beryllium chalcogenide

A detailed theoretical study of structural, electronic and Vibrational properties of BeX compound is presented by performing ab-initio calculations based on density-functional theory using the Espresso package. The calculated value of lattice constant and bulk modulus are compared with the available experimental and other theoretical data and agree reasonably well. BeX (X = S,Se,Te) compounds in the ZB phase are indirect wide band gap semiconductors with an ionic contribution. The phonon dispersion curves are represented which shows that these compounds are dynamically stable in ZB phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Comment on “Rethinking first-principles electron transport theories with projection operators: The problems caused by partitioning the basis set” [J. Chem. Phys. 139, 114104 (2013)]

In a recent paper Reuter and Harrison [J. Chem. Phys. 139, 114104 (2013)] question the widely used mean-field electron transport theories, which employ nonorthogonal localized basis sets. They claim these can violate an “implicit decoupling assumption,” leading to wrong results for the current, different from what would be obtained by using an orthogonal basis, and dividing surfaces defined in real-space. We argue that this assumption is not required to be fulfilled to get exact results. We show how the current/transmission calculated by the standard Greens function method is independent of whether or not the chosen basis set is nonorthogonal, and that the current for a given basis set is consistent with divisions in real space. The ambiguity known from charge population analysis for nonorthogonal bases does not carry over to calculations of charge flux.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Response to “Comment on ‘Rethinking first-principles electron transport theories with projection operators: The problems caused by partitioning the basis set’” [J. Chem. Phys. 140, 177103 (2014)]

The thesis of Brandbyge's comment [J. Chem. Phys. 140, 177103 (2014)] is that our operator decoupling condition is immaterial to transport theories, and it appeals to discussions of nonorthogonal basis sets in transport calculations in its arguments. We maintain that the operator condition is to be preferred over the usual matrix conditions and subsequently detail problems in the existing approaches. From this operator perspective, we conclude that nonorthogonal projectors cannot be used and that the projectors must be selected to satisfy the operator decoupling condition. Because these conclusions pertain to operators, the choice of basis set is not germane.

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

First principles investigations on the electronic structure of anchor groups on ZnO nanowires and surfaces

We report on density functional theory investigations of the electronic properties of monofunctional ligands adsorbed on ZnO-(1010) surfaces and ZnO nanowires using semi-local and hybrid exchange-correlation functionals. We consider three anchor groups, namely thiol, amino, and carboxyl groups. Our results indicate that neither the carboxyl nor the amino group modify the transport and conductivity properties of ZnO. In contrast, the modification of the ZnO surface and nanostructure with thiol leads to insertion of molecular states in the band gap, thus suggesting that functionalization with this moiety may customize the optical properties of ZnO nanomaterials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

A first principles analysis of the effect of hydrogen concentration in hydrogenated amorphous silicon on the formation of strained Si-Si bonds and the optical and mobility gaps

In this paper, we use a model of hydrogenated amorphous silicon generated from molecular dynamics with density functional theory calculations to examine how the atomic geometry and the optical and mobility gaps are influenced by mild hydrogen oversaturation. The optical and mobility gaps show a volcano curve as the hydrogen content varies from undersaturation to mild oversaturation, with largest gaps obtained at the saturation hydrogen concentration. At the same time, mid-gap states associated with dangling bonds and strained Si-Si bonds disappear at saturation but reappear at mild oversaturation, which is consistent with the evolution of optical gap. The distribution of Si-Si bond distances provides the key to the change in electronic properties. In the undersaturation regime, the new electronic states in the gap arise from the presence of dangling bonds and strained Si-Si bonds, which are longer than the equilibrium Si-Si distance. Increasing hydrogen concentration up to saturation reduces the strained bonds and removes dangling bonds. In the case of mild oversaturation, the mid-gap states arise exclusively from an increase in the density of strained Si-Si bonds. Analysis of our structure shows that the extra hydrogen atoms form a bridge between neighbouring silicon atoms, thus increasing the Si-Si distance and increasing disorder in the sample.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Oxygen and nitrogen diffusion in α-hafnium from first principles

We use a combination of density functional theory and multistate diffusion formalism to analyze the diffusion of oxygen and nitrogen in technologically important hafnium metal. Comparing the local density approximation and the Perdew-Burke-Ernzerhof version of the generalized gradient approximation, we find that a better description of the hafnium lattice in the latter results in the correct sequence of stable and transition states for oxygen interstitials leading to essentially quantitative agreement with experiment. For oxygen diffusion, we find an isotropic temperature-dependent diffusion coefficient of D=0.082e{sup −2.04/k{sub B}T}cm{sup 2}s{sup −1} utilizing interstitial sites with hexahedral and octahedral coordination. For the diffusivity of nitrogen, we find that an additional stable interstitial site, the crowdion site, exists and that the diffusion coefficient is D=0.15e{sup −2.68/k{sub B}T}cm{sup 2}s{sup −1}. Our results also reproduce the experimental observation that nitrogen diffusivity is lower than that of oxygen in hafnium.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

(Sr,Ba)(Si,Ge){sub 2} for thin-film solar-cell applications: First-principles study

In order to meet the increasing demand for electric power generation from solar energy conversion, the development of efficient light absorber materials has been awaited. To this end, the electronic and optical properties of advanced alkaline-earth-metals disilicides and digermanides (SrSi{sub 2}, BaSi{sub 2}, SrGe{sub 2}, and BaGe{sub 2}) are studied by means of the density functional theory using HSE06 exchange-correlation energy functional. Our calculations show that all these orthorhombic structured compounds have fundamental indirect band gaps in the range E{sub g} ≈ 0.89–1.25 eV, which is suitable for solar cell applications. The estimated lattice parameters and band gaps are in good agreement with experiments. Our calculations show that the electronic band structures of all four compounds are very similar except in the vicinity of the Γ-point. The valence band of these compounds is made up by Si(Ge)-p states, whereas the conduction band is composed of Sr(Ba)-d states. Their band alignments are carefully determined by estimating the work function of each compound using slab model. The optical properties are discussed in terms of the complex dielectric function ε(ω) = ε{sub 1}(ω) + iε{sub 2}(ω). The static and high-frequency dielectric constants are calculated, taking into account the ionic contribution. The absorption coefficient α(ω) demonstrates that a low energy dispersion of the conduction band, which results in a flat conduction band minimum, leads to large optical activity in these compounds. Therefore, alkaline-earth-metals disilicides and digermanides possess great potential as light absorbers for applications in thin-film solar cell technologies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

First-principles calculations of the indigo encapsulation and adsorption by MgO nanotubes

We have performed ab-initio calculations to investigate the structural and electronic properties of (m,m) chiral magnesium oxide nanotubes, (m,m)MgONTs, to explore the encapsulation, inclusion, and adsorption of dyes (organic molecules) such as Indigo (IND). Studies start by determining the structural parameters of the MgO nanotubes with different diameters and the IND. The indigo encapsulation into the MgONT is studied considering four (m,m) chiralities which yield 4 different NT diameters. In the endohedral functionalization, the indigo is within the NT at a tilt angle as in previous theoretical studies of organic molecules inside carbon and boron-nitride nanotubes. Results show that the encapsulation is a strong exothermic process with the m = 6 case exhibiting the largest encapsulation energy. It is also explored the indigo adsorption on the NT surface in the parallel and perpendicular configurations. The perpendicular configuration of the IND adsorption on the (8,8)MgONT exhibits the largest energy. The indigo inclusion within the NTs meets a potential barrier when m < 6, however this barrier diminishes as the index increases. Additionally, we have determined the total density of states (DOS), partial DOS, electron charge redistributions, and the highest occupied molecular orbital–lowest unoccupied molecular orbital levels for the NTs with m = 6. Very strong binding energies and electron charge transfer from the IND to NTs is present in the atomic structures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Half-metallicity modulation of hybrid BN-C nanotubes by external electric fields: A first-principles study

On the basis of density functional theory, we systematically investigate the electronic and magnetic properties of hybrid BN-C nanotubes, C{sub x}(BN){sub y} where x + y = 12, with and without an external electric field. The BN-C nanotubes are totally distinct from pristine boron-nitride and carbon nanotubes. The electronic properties of C{sub x}(BN){sub y} change significantly with composition: from the nonmagnetic semiconductors to the half-metals. The half-metallicity is attributed to the competition among the band gap, which is related to the width of C domain, the width of BN domain, and the intrinsic polarization field. Application of the external fields can enhance or counterbalance the polarization fields and change the band gaps. The half-metallicity can be modulated. In BN-rich tubes, such as C{sub 2}(BN){sub 10}, the energy gap can be engineered from 0.50 eV to 0.95 eV and in C{sub 3}(BN){sub 9}, the ground state is converted from the nonmagnetic state into the anti-ferro-magnetic one. In other tubes, the half-metallicity can be enhanced or destroyed by different external fields. The modulation indicates that hybrid BN-C nanotubes can work as the components of the spin-filter devices.

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

D{sup 0} magnetism in Ca doped narrow carbon nanotubes: First principle chirality effect study

Curvature has always had crucial effects on the physical properties of narrow carbon nanotubes (CNTs) and here spin-polarized density functional calculations were employed to study electronic and magnetic properties of calcium-decorated narrow (5,5) and (9,0)CNTs with close diameters (∼7 Å) and different chiralities. Our results showed that chirality had great impact on the electronic structure and magnetization of the doped CNTs. In addition, internally or externally doping of the calcium atoms was studied comparatively and although for the (9,0)CNT the internal doping was the most stable configuration, which involves a novel kind of spin-polarization originated from Ca-4s electrons, but for the (5,5)tube the external doping was the most stable one without any spin-polarization. On the other hand, calcium doping in the center of the (5,5)CNT was an endothermic process and led to the spin-polarization of unoccupied Ca-3d orbitals via direct exchange interaction between adjacent Ca atoms. In the considered systems, the existence of magnetization in the absence of any transition-metal elements was an example of valuable d{sup 0} magnetism title.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

First principles studies of proton conduction in KTaO{sub 3}

KTaO{sub 3} (KTO) is a useful prototypical perovskite for examining the mechanisms of proton transport in perovskites. Previously, Gomez et al. [J. Chem. Phys. 126, 194701 (2007)] reported density functional theory (DFT) calculations describing proton hopping in defect-free KTO. We use DFT calculations to extend that work in two directions, namely, understanding isotope effects in low and high temperature proton transport and the role of native point defects in KTO. At cryogenic temperatures, quantum tunneling plays a vital role in the net hopping of protons in KTO. At the elevated temperature characteristic of applications involving proton-conducting perovskites, tunneling is negligible but zero point energy effects still lead to non-negligible isotope effects for H{sup +}, D{sup +}, and T{sup +}. We also use DFT to characterize the populations of relevant point defects in KTO as a function of experimental conditions, and to examine the migration of protons that are close in proximity to these defects. This information gives useful insight into the overall transport rates of protons through KTO under a variety of external environments. We also assess the overall diffusivity of protons in KTO at various ranges of oxygen vacancy concentrations by performing kinetic Monte Carlo simulations.

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

The formation and electronic properties of hydrogenated bilayer silicene from first-principles

Density-functional calculations of the formation and electronic properties of bilayer silicene and hydrogenated bilayer silicene are present. The structure optimization and phonon calculations are carried out to demonstrate that bilayer silicene has stable structure with AB stacking and preserves the linear energy dispersions near the K and K′ points in the hexagonal Brillouin zone, and our results agree well with the previous calculations. Based on the symmetry of bilayer silicene, we study the stability of four hydrogenated bilayer silicene by the phonon-mode analysis. The configurations of semihydrogenated one-layer and semihydrogenated double-layer are confirmed as dynamically stable with no imaginary phonon frequencies. The case of semihydrogenated one-layer shows ferromagnetic ground state due to the unpaired 3p electrons, while that of semihydrogenated double-layer is predicted to be a indirect band gap semiconductor with nonmagnetic ground state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Thermodynamic stability and structures of iron chloride surfaces: A first-principles investigation

In this study, we report a comprehensive density functional theory investigation of the structure and thermodynamic stability of FeCl{sub 2} and FeCl{sub 3} surfaces. Calculated lattice constants and heats of formation for bulk FeCl{sub 2} and FeCl{sub 3} were found to be in relatively good agreement with experimental measurements. We provide structural parameters for 15 distinct FeCl{sub 2} and FeCl{sub 3} surfaces along the three low-index orientations. The optimized geometries for all surfaces are compared with analogous bulk values. Ab initio atomistic thermodynamic calculations have been carried out to assess the relative thermodynamic stability of FeCl{sub 2} and FeCl{sub 3} surfaces under practical operating conditions of temperatures and pressures. The FeCl{sub 2} (100-Cl) surface is found to afford the most stable configuration at all experimentally accessible gas phase conditions.

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

First-principles studies on graphene-supported transition metal clusters

Theoretical studies on the structure, stability, and magnetic properties of icosahedral TM{sub 13} (TM = Fe, Co, Ni) clusters, deposited on pristine (defect free) and defective graphene sheet as well as graphene flakes, have been carried out within a gradient corrected density functional framework. The defects considered in our study include a carbon vacancy for the graphene sheet and a five-membered and a seven-membered ring structures for graphene flakes (finite graphene chunks). It is observed that the presence of defect in the substrate has a profound influence on the electronic structure and magnetic properties of graphene-transition metal complexes, thereby increasing the binding strength of the TM cluster on to the graphene substrate. Among TM{sub 13} clusters, Co{sub 13} is absorbed relatively more strongly on pristine and defective graphene as compared to Fe{sub 13} and Ni{sub 13} clusters. The adsorbed clusters show reduced magnetic moment compared to the free clusters.

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

Effect of tensile strain on the electronic structure of Ge: A first-principles calculation

Taking the change of L-point conduction band valley degeneracy under strain into consideration, we investigate the effect of biaxially tensile strain (parallel to the (001), (110), and (111) planes) and uniaxially tensile strain (along the [001], [110], and [111] directions) on the electronic structure of Ge using density functional theory calculations. Our calculation shows that biaxial tension parallel to (001) is the most efficient way to transform Ge into a direct bandgap material among all tensile strains considered. [111]-tension is the best choice among all uniaxial approaches for an indirect- to direct-bandgap transition of Ge. The calculation results, which are further elaborated by bond-orbital approximation, provide a useful guidance on the optical applications of Ge through strain engineering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Direct first-principles simulation of a high-performance electron emitter: Lithium-oxide-coated diamond surface

We examined the field emission properties of lithium(Li)/oxygen(O)-co-terminated diamond (001) surface [C(001)-LiO] through real-time electron dynamics simulation under an applied field. The current emitted from this surface was found to be more than four-fold that emitted by an H-terminated (001) surface, the latter being a typical negative electron affinity system. This high performance is attributed to the Li layer, which bends the potential wall of O-induced electron pockets down in the direction of vacuum, thus facilitating electron emission. Detailed analysis of the emitted electrons and the profile of the self-consistent potential elucidated that the role of O atoms changes from an electron barrier on OH-terminated diamond surfaces to an outlet for electron emission on C(001)-LiO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

First principles transport coefficients and reaction rates of Ar{sub 2}{sup +} ions in argon for cold plasma jet modeling

Momentum-transfer collision cross-sections and integral collision cross-sections for the collision-induced dissociation are calculated for collisions of ionized argon dimers with argon atoms using a nonadiabatic semiclassical method with the electronic Hamiltonian calculated on the fly via a diatomics-in-molecules semiempirical model as well as inverse-method modeling based on simple isotropic rigid-core potential. The collision cross-sections are then used in an optimized Monte Carlo code for evaluations of the Ar{sub 2}{sup +} mobility in argon gas, longitudinal diffusion coefficient, and collision-induced dissociation rates. A thorough comparison of various theoretical calculations as well as with available experimental data on the Ar{sub 2}{sup +} mobility and collision cross-sections is performed. Good agreement is found between both theoretical approaches and the experiment. Analysis of the role of inelastic processes in Ar{sub 2}{sup +}/Ar collisions is also provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗