Electronic structure of microporous titanosilicate ETS-10

The electronic structure of a microporous titanosilicate framework, ETS-10 is calculated by means of a first-principles self-consistent method. It is shown that without the inclusion of the alkali atoms whose positions in the framework are unknown, ETS-10 is an electron deficient system with 32 electrons per unit cell missing at the top of an otherwise semiconductor-like band structure. The calculated density of slates are resolved into partial components. It is shown that the states of the missing electrons primarily originate from the Ti-O bond. The local density of states of the Ti-3d orbitals in the ETS-10 framework is quite different from the perovskite BaTiO3. The possibilities of ETS-10 crystal being ferroelectric or having other interesting properties are discussed.

A theoretical study of the effects of lithium intercalation on the electronic structure of TiS

The band structure of the intercalation complex of LiTiS has been computed using a semi-empirical tight-binding method and this is compared with the results of a revised TiS calculation. The results obtained confirm that changes in the basic electrical characteristics of TiS, which occur when it is intercalated with lithium, can be attributed to a rigid-band filling of its lowest unoccupied electron states as has previously been proposed. However, they also suggest that intercalation can act to alter the nature and the dispersion of some of the energy bands in the unintercalated crystal. The bands which are most affected by the process are those which derive from orbitals which have the same symmetry as the lithium 2s orbital, namely, the titanium 4s conduction level and the tightly bound sulphur 3s levels.

Spin-polarized electronic-structure of MnBiAl

The self-consistent spin-polarized band-structure calculation of ferromagnetic compound MnBiAl in its low-temperature phase has been performed. In this paper the calculation results are given. Comparison with the results of MnBi is performed in order to find the effect on electronic structure by doping with Al.

Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.

Electronic structure and optical properties of BaMoO(4) powders

Barium molybdate (BaMoO(4)) powders were synthesized by the co-precipitation method and processed in microwave-hydrothermal at 140 degrees C for different times. These powders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis) absorption spectroscopies and photoluminescence (PL) measurements. XRD patterns and FT-Raman spectra showed that these powders present a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 850.4 cm(-1), which is associated to the Mo-O antisymmetric stretching vibrations into the [MoO(4)] clusters. UV-vis absorption spectra indicated a reduction in the intermediary energy levels within band gap with the processing time evolution. First-principles quantum mechanical calculations based on the density functional theory were employed in order to understand the electronic structure (band structure and density of states) of this material. The powders when excited with different wavelengths (350 nm and 488 nm) presented variations. This phenomenon was explained through a model based in the presence of intermediary energy levels (deep and shallow holes) within the band gap. (C) 2009 Elsevier B.V. All rights reserved.

Electronic structure and optical properties of BaMoO4 powders

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A combined theoretical and experimental study of electronic structure and optical properties of β-ZnMoO4 microcrystals

In this paper, a combined theoretical and experimental study on the electronic structure and photoluminescence (PL) properties of beta zinc molybdate (β-ZnMoO4) microcrystals synthesized by the hydrothermal method has been employed. These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, Fourier transform Raman (FT-Raman) and Fourier transform infrared (FT-IR) spectroscopies. Their optical properties were investigated by ultraviolet-visible (UV-Vis) absorption spectroscopy and PL measurements. First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level have been carried out. XRD patterns, Rietveld refinement, FT-Raman and FT-IR spectra showed that these crystals have a wolframite-type monoclinic structure. The Raman and IR frequencies experimental results are in reasonable agreement with theoretically calculated results. UV-Vis absorption measurements shows an optical band gap value of 3.17 eV, while the calculated band structure has a value of 3.22 eV. The density of states indicate that the main orbitals involved in the electronic structure of β-ZnMoO4 crystals are (O 2p-valence band and Mo 4d-conduction band). Finally, PL properties of β-ZnMoO4 crystals are explained by means of distortions effects in octahedral [ZnO6] and [MoO6] clusters and inhomogeneous electronic distribution into the lattice with the electron density map. © 2013 Elsevier Ltd. All rights reserved.

Local electronic structure, optical bandgap and photoluminescence (PL) properties of Ba(Zr0.75Ti0.25)O3 powders

Ba(Zr0.75Ti0.25)O3 (BZT-75/25) powders were synthesized by the polymeric precursor method. Samples were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques. Their electronic structures were evaluated by first-principle quantum mechanical calculations based on density functional theory at the B3LYP level. Their optical properties were investigated by ultraviolet-visible (UV-Vis) spectroscopy and photoluminescence (PL) measurements at room temperature. XRD patterns and Rietveld refinement data indicate that the samples have a cubic structure. XANES spectra confirm the presence of pyramidal [TiO5] clusters and octahedral [TiO6] clusters in the disordered BZT-75/25 powders. EXAFS spectra indicate distortion of Ti-O and Ti-O-Ti bonds the first and second coordination shells, respectively. UV-Vis absorption spectra confirm the presence of different optical bandgap values and the band structure indicates an indirect bandgap for this material. The density of states demonstrates that intermediate energy levels occur between the valence band (VB) and the conduction band (CB). These electronic levels are due to the predominance of 4d orbitals of Zr atoms in relation to 3d orbitals of Ti atoms in the CB, while the VB is dominated by 2p orbitals related to O atoms. There was good correlation between the experimental and theoretical optical bandgap values. When excited at 482 nm at room temperature, BZT-75/25 powder treated at 500 C for 2 h exhibited broad and intense PL emission with a maximum at 578 nm in the yellow region. © 2013 Elsevier Ltd. All rights reserved.

Experimental and Theoretical Investigations of Electronic Structure and Photoluminescence Properties of beta-Ag2MoO4 Microcrystals

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Molecular and Electronic Structure of the Peptide Subunit of Geobacter sulfurreducens Conductive Phi from First Principles

The respiration of metal oxides by the bacterium Geobacter sulfurreducens requires the assembly of a small peptide (the GS pilin) into conductive filaments termed pili. We gained insights into the contribution of the GS pilin to the pilus conductivity by developing a homology model and performing molecular dynamics simulations of the pilin peptide in vacuo and in solution. The results were consistent with a predominantly helical peptide containing the conserved a-helix region required for pilin assembly but carrying a short carboxy-terminal random-coiled segment rather than the large globular head of other bacterial pilins. The electronic structure of the pain was also explored from first principles and revealed a biphasic charge distribution along the pilin and a low electronic HOMO-LUMO gap, even in a wet environment. The low electronic band gap was the result of strong electrostatic fields generated by the alignment of the peptide bond dipoles in the pilin's alpha-helix and by charges from ions in solution and amino acids in the protein. The electronic structure also revealed some level of orbital delocalization in regions of the pilin containing aromatic amino acids and in spatial regions of high resonance where the HOMO and LUMO states are, which could provide an optimal environment for the hopping of electrons under thermal fluctuations. Hence, the structural and electronic features of the pilin revealed in these studies support the notion of a pilin peptide environment optimized for electron conduction.

Electronic structure of copper nitrides as a function of nitrogen content

he nitrogen content dependence of the electronic properties for copper nitride thin films with an atomic percentage of nitrogen ranging from 26 ± 2 to 33 ± 2 have been studied by means of optical (spectroscopic ellipsometry), thermoelectric (Seebeck), and electrical resistivity measurements. The optical spectra are consistent with direct optical transitions corresponding to the stoichiometric semiconductor Cu3N plus a free-carrier contribution, essentially independent of temperature, which can be tuned in accordance with the N-excess. Deviation of the N content from stoichiometry drives to significant decreases from − 5 to − 50 μV/K in the Seebeck coefficient and to large enhancements, from 10− 3 up to 10 Ω cm, in the electrical resistivity. Band structure and density of states calculations have been carried out on the basis of the density functional theory to account for the experimental results.

Nanocontacts: probing electronic structure under extreme uniaxial strains

Nanometer-sized metallic necks have the unique ability to sustain extreme uniaxial loads (about 20 times greater than the bulk material). We present an experimental and theoretical study of the electronic transport properties under such extreme conditions. Conductance measurements on gold and aluminum necks show a strikingly different behavior: While gold shows the expected conductance decrease with increasing elastic elongation of the neck, aluminum necks behave in the opposite way. We have performed first-principles electronic-structure calculations which reproduce this behavior, showing that it is an intrinsic property of the bulk band structure under high uniaxial strain.

Theory of strongly correlated electron systems. II. Including correlation effects into electronic structure calculations

We have previously shown that a division of the f-shell into two subsystems gives a better understanding of the cohesive properties as well the general behavior of lanthanide systems. In this article, we present numerical computations, using the suggested method. We show that the picture is consistent with most experimental data, e.g., the equilibrium volume and electronic structure in general. Compared with standard energy band calculations and calculations based on the self-interaction correction and LIDA + U, the f-(non-f)-mixing interaction is decreased by spectral weights of the many-body states of the f-ion. (c) 2005 Wiley Periodicals, Inc.

Unoccupied electronic states in NiS2-xSex across the metal-insulator transition

We investigate the evolution of the electronic structure across the insulator-metal transition in NiS2-xSex with changing composition, but in the absence of any structural or magnetic changes. A comparison of the inverse photoemission spectra with band-structure calculations establishes the importance of correlation effects in these systems. Systematic changes in the spectral distribution establish the persistence of the upper Hubbard band well into the metallic regime, with the insulator-to-metal transition being driven by a transfer of spectral weight from the Hubbard band to states close to the Fermi energy.

k.p based closed form energy band gap and transport electron effective mass model for 100] and 110] relaxed and strained Silicon nanowire

In this paper, we address a physics based closed form model for the energy band gap (E-g) and the transport electron effective mass in relaxed and strained 100] and 110] oriented rectangular Silicon Nanowire (SiNW). Our proposed analytical model along 100] and 110] directions are based on the k.p formalism of the conduction band energy dispersion relation through an appropriate rotation of the Hamiltonian of the electrons in the bulk crystal along 001] direction followed by the inclusion of a 4 x 4 Luttinger Hamiltonian for the description of the valance band structure. Using this, we demonstrate the variation in Eg and the transport electron effective mass as function of the cross-sectional dimensions in a relaxed 100] and 110] oriented SiNW. The behaviour of these two parameters in 100] oriented SiNW has further been studied with the inclusion of a uniaxial strain along the transport direction and a biaxial strain, which is assumed to be decomposed from a hydrostatic deformation along 001] with the former one. In addition, the energy band gap and the effective mass of a strained 110] oriented SiNW has also been formulated. Using this, we compare our analytical model with that of the extracted data using the nearest neighbour empirical tight binding sp(3)d(5)s* method based simulations and has been found to agree well over a wide range of device dimensions and applied strain. (C) 2012 Elsevier Ltd. All rights reserved.