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.

Pressure dependence of the electronic subband structure of strained In0.2Ga0.8As/GaAs MQWs

We have measured low-temperature photoluminescence (PL) and optical absorption spectra of an In0.2Ga0.8As/GaAs multiple quantum well (MQW) structure at pressures up to 8 GPa. Below 4.9 GPa, PL shows only the emission of the n = 1 heavy-hole (HH) exciton. Three new X-related PL bands appear at higher pressures. They are assigned to spatially indirect (type-II) and direct (type-I) transitions from X(Z) states in GaAs and X(XY) valleys of InGaAs, respectively, to the HH subband of the wells. From the PL data we obtain a valence band offset of 80 meV for the strained In0.2Ga0.8As/GaAs MQW system. Absorption spectra show three features corresponding to direct exciton transitions in the quantum wells. In the pressure range of 4.5 to 5.5 GPa an additional pronounced feature is apparent in absorption, which is attributed to the pseudo-direct transition between a HH subband and the folded X(Z) states of the wells. This gives the first clear evidence for an enhanced strength of indirect optical transitions due to the breakdown of translational invariance at the heterointerfaces in MQWs.

Electronic structure of quantum spheres and quantum wires

The electronic structures of quantum spheres and quantum wires are studied in the framework of the effective-mass theory. The spin-orbital coupling (SOC) effect is taken into account. On the basis of the zero SOC limit and strong SOC limit the hole quantum energy levels as functions of SOC parameter lambda are obtained. There is a fan region in which the ground and low-lying excited states approach those in the strong SOC limit as lambda increases. Besides, some theoretical results on the corrugated superlattices (CSL) are given.

Electronic structures of the zinc-blende GaN/Ga1-xAlxN compressively strained superlattices and quantum wells

The electronic structures of the zinc-blende GaN/Ga0.85Al0.15N compressively strained superlattices and quantum wells are investigated using a 6 x 6 Hamiltonian model (including the heavy hole, light hole and spin-orbit splitting band). The energy bands, wavefunctions and optical transition matrix elements are calculated. It is found that the light hole couples with the spin-orbit splitting state even at the k=0 point, resulting in the hybrid states. The heavy hole remains a pure heavy hole state at k=0. The optical transitions from the hybrid valence states to the conduction states are determined by the transitions of the light hole and spin-orbit splitting states to the conduction states. The transitions from the heavy hole, light hole and spin-orbit splitting states to the conduction states obey the selection rule Delta n=0. The band structures obtained in this work will be valuable in designing GaN/GaAlN based optoelectronic devices. (C) 1996 Academic Press Limited

Verification of EL2 electronic absorption effect on charge transfer in semi-insulating GaAs

The electronic absorption of EL2 centers has been clarified to be related to the electron acid hole photoionizations, and the transition from its ground state to metastable state, respectively. Under an illumination with a selected photon energy in the near infrared region, these three processes with different optical cross sections will show different kinetics against the illumination time. It has recently been shown that the photosensitivity (measured under 1.25 eV illumination) of the local vibrational mode absorption induced by some deep defect centers in SI-GaAs is a consequence of the electron and hole photoionizations of EL2. This paper directly measures the kinetics of the electronic transition associated with EL2 under 1.25 eV illumination, which implies the expected charge transfer among different charge states of the EL2 center. A calculation based on a simple rate equation model is in good agreement with the experimental results.

ELECTRON-STATES OF A VACANCY IN THE CORE OF THE 90-DEGREES PARTIAL DISLOCATION IN SILICON

An LCAO scheme (linear combination of atomic orbitals) taking into account ten atomic orbitals (s-, p-, and d-type) is used to calculate the electronic structure of a vacancy present in the core of the reconstructed 90 degrees partial dislocation in silicon. The levels in the band gap are extracted using Lanczos' algorithm and a continued fraction representation of the local density of states. The three-fold degenerate stale of the ideal vacancy is split into three levels with energies 0.26, 1.1, and 1.9 eV measured from the valence band edge.

Electronic investigation of self-organized InAs quantum dots

Deep Level Transient Spectroscopy (DLTS) has been applied to investigate the electronic properties of self-organized InAs quantum dots. The energies of electronic ground states of 2.5ML and 1.7ML InAs quantum dots (QDs) with respect to the conduction band of bulk GaAs are about 0.21 eV and 0.09 eV, respectively. We have found that QDs capture electrons by lattice relaxation through a multi-phonon emission process. The samples are QDs embedded in superlattices with or without a 500 Angstrom GaAs spacing layer between every ten periods of a couple of GaAs and InAs layers. The result shows that the density of dislocations in the samples with spacer layers is much lower than in the samples without the spacer layers.

DFT/TDDFT Studies on the Electronic Structures and Spectral Properties of Rhenium(I) Pyridinybenzoimidazole Complexes

The electronic structures and spectral properties of three Re(I) complexes [Re(CO)(3)XL] (X = Br, Cl; L = 1-(4-5 '-phenyl-1.3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (1), 1-(4-carbazolylbutyl)-2-pyridinylbenzoimidazole (2), and 2-(1-ethyl benzimidazol-2-yl)pyridi ne (3)) were investigated theoretically. The ground and the lowest lying triplet excited states were full optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. TDDFT/PCM calculations have been employed to predict the absorption and emission spectra starting from the ground and excited state geometries, respectively.

Ab initio study on the electronic, magnetic, and mechanical properties of CaCu3V4O12

The electronic, magnetic, and mechanical properties of CaCu3V4O12 are investigated by use of the density functional theory method. The calculated results indicate that CaCu3V4O12 is a half-metallic and ferrimagnetic compound. The magnetic coupling for Cu-V is antiferromagnetic, while those for Cu-Cu and V-V are ferromagnetic. The obtained elastic constants suggest that the compound is mechanically stable. The calculated oxidation states and density of states reveal the existence of a mixed valence for Cu and V. This supports the experimental observation of the mixed valence in Ca2+Cu2+Cu2+(V25+V24+)O-12.

Chemical Bonding and Electronic Structure of 4d-Metal Monosulfides

Bond distances, vibrational frequencies, dissociation energies, electron affinities, ionization potentials and dipole moments of the title molecules in neutral and charged ions were studied by use of density functional method. Ground states for each molecule were assigned. The calculated bond distance decreases with the increasing of atomic number of 4d metals, reaches minimum at RhS, then increases. For cationic molecules, the calculated bond distance decreases to the minimum at MoS+, then increases. The calculated vibrational frequency decreases from YS(YS+) to PdS(PdS+) for both neutral and cationic molecules. The bond ionic character decreases from YS(YS+) to PdS(PdS+) for neutral and cationic molecules. The bonding patterns are discussed and compared with the available studies.

Pressure Effects on the Structural, Electronic, and Optical Properties of Si-n@SWCNTs

Well-ordered single, double/four parallel, three/four-strands helical chains, and five-strand helical chain with a single atom chain at the center of Si nanowires (NWs) inside single-walled carbon nanotubes (Si-n@SWCNTs) are obtained by means of molecular dynamics. On the basis of these optimized structures, the structural evolution of Si-n@SWCNTs subjected to axial stress at low temperature is also investigated. Interestingly, the double parallel chains depart at the center and transform into two perpendicular parts, the helical shell transformed into chain, and the strand number of Si NWs increases during the stress load. Through analyzis of pair correlation function (PCF), the density of states (DOS), and the z-axis polarized absorption spectra of Si-n@SWCNTs, we find that the behavior of Si-n@SWCNTs under stress strongly depends on SWCNTs' symmetry, diameter, as well as the shape of Nws, which provide valuable information for potential application in high pressure cases such as seabed cable.

Electronic structures and chemical bonding in 4d transition metal monohalides

Bond distances, vibrational frequencies, dipole moments, dissociation energies, electron affinities, and ionization potentials of NIX (XM = Y-Cd, X = F, Cl, Br, I) molecules in neutral, positively, and negatively charged ions were studied by density functional method, B3LYP. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the 4d transition metal s, d orbitals, and the p orbital of halogen. For both neutral and charged molecules, the fluorides have the shortest bond distance, iodides the longest. Although the opposite situation is observed for vibrational frequency, that is, fluorides have the largest value, iodides the smallest. For neutral and anionic species, the dissociation energy tends to decrease with the increasing atomic number from Y to Cd, suggesting the decreasing or weakening of the bond strength. For cationic species, the trend is observed from Y to Ag.

Electronic structures of 5d transition metal monoxides by density functional theory

Bond distances, vibrational frequencies, electron affinities, ionization potentials, and dissociation energies of the diatomic 5d transition metal (except La) monoxides and their positively and negatively charged ions were studied by use of density functional methods B3LYP, BLYP, B3PW91, BPW91, B3P86, BP86, MPW1PW91, PBE1PBE, and SVWN. Our calculation shows that for each individual species, the calculated properties are quite sensitive to the method used. Compared with hybrid density functional method B3PW91 (B3P86), pure density functional method BPW91 (BP86) gives longer bond distance (lower vibrational frequency) from HfO to PtO for neutral species, HfO+ to IrO+ for cationic species, and HfO- to AuO- for anionic species. While for B3LYP and BLYP, the trend was observed for cationic species from HfO+ to IrO+ and anionic species from HfO- to AuO- (except TaO-), but not for neutrals. Pure density function methods BLYP, BPW91, and BP86 give larger dissociation energy compared with hybrid density functional methods B3LYP, B3PW91, and B3P86. SVWN in most cases gives the smallest bond distance, while BLYP gives the largest value. MPW1PW91 and PBE1PBE show the same performance in predicting the spectroscopic constants.

Trends in elasticity and electronic structure of 5d transition metal diborides: first-principles calculations

We investigate the cohesive energy, heat of formation, elastic constant and electronic band structure of transition metal diborides TMB2 (TM = Hf, Ta, W, Re, Os and Ir, Pt) in the Pmmn space group using the ab initio pseudopotential total energy method. Our calculations indicate that there is a relationship between elastic constant and valence electron concentration (VEC): the bulk modulus and shear modulus achieve their maximum when the VEC is in the range of 6.8-7.2. In addition, trends in the elastic constant are well explained in terms of electronic band structure analysis, e.g., occupation of valence electrons in states near the Fermi level, which determines the cohesive energy and elastic properties. The maximum in bulk modulus and shear modulus is attributed to the nearly complete filling of TM d-B p bonding states without filling the antibonding states. On the basis of the observed relationship, we predict that alloying W and Re in the orthorhombic structure OsB2 might be harder than alloying the Ir element. Indeed, the further calculations confirmed this expectation.

Electronic structures of Al2W, AlW2 clusters and their anions

Possible structures for Al2W and AlW2 clusters and their anions were presented and studied by use of density functional theory B3LYP at various spin multiplicities. The proposed three structures are triangular form with C-2v symmetry; linear structure with D (infinity h) symmetry; and linear structure with C (infinity v) symmetry. The calculated results indicate that structures with C-2v symmetry are the most stable for both neutral clusters and their anions. For Al2W, C-2v Symmetry at spin multiplicity 5 is the ground state, while for its anion, doublet is the lowest. For AlW2 and its anion, doublet and triplet are the ground states, respectively.