Electronic structure of early 3d-transition-metal oxides by analysis of the 2p core-level photoemission spectra

The electronic structures of a wide range of early transition-metal (TM) compounds, including Ti and V oxides with metal valences ranging from 2+ to 5+ and formal d-electron numbers ranging from 0 to 2, have been investigated by a configuration-interaction cluster model analysis of the core-level metal 2p x-ray photoemission spectra (XPS). Inelastic energy-loss backgrounds calculated from experimentally measured electron-energy-loss spectra (EELS) were subtracted from the XPS spectra to remove extrinsic loss features. Parameter values deduced for the charge-transfer energy Delta and the d-d Coulomb repulsion energy U are shown to continue the systematic trends established previously for the late TM compounds, giving support to a charge-transfer mechanism for the satellite structures. The early TM compounds are characterized by a large metal d-ligand p hybridization energy, resulting in strong covalency in these compounds. Values for Delta and U suggest that many early TM compounds should be reclassified as intermediate between the charge-transfer regime and the Mott-Hubbard regime.

meso-substituted octabromoporphyrins: Synthesis, spectroscopy, electrochemistry and electronic structure

The free-base, copper(II) and zinc(II) derivatives of 5,10,15,20-tetraarylporphyrin (aryl = phenyl, 4-methylphenyl or 4-chlorophenyl) and the corresponding brominated 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraarylporphyrin derivatives have been synthesized and their spectral and redox properties compared by UV/VIS, H-1 NMR, ESR and cyclic voltammetric methods. Substitution with the electron-withdrawing bromine groups at the pyrrole carbons has a profound influence on the UV/VIS and H-1 NMR spectral features and also on the redox potentials of these systems. On the other hand, electron-withdrawing chloro or electron-donating methyl groups at the para positions of the four phenyl rings have only a marginal effect on the spectra and redox potentials of both the brominated and the non-brominated derivatives. The ESR data for the copper(II) derivatives of ail these systems reveal that substitution at either the beta-pyrrole carbons and/or the para positions of the meso-phenyl groups does not significantly affect the spin-Hamiltonian parameters that describe the metal centre in each case. Collectively, these observations suggest that the highest-occupied (HOMO) and lowest-unoccupied molecular orbitals (LUMO) of the octabromoporphyrins involve the porphyrin pi-ring system as is the case with the non-brominated derivatives.-Investigations have been carried out to probe the electronic structures of these systems by three different approaches involving spectral and redox potential data as well as AMI calculations. The results obtained suggest that the electron-withdrawing beta-bromine substituents stabilize the LUMOs and, to a lesser degree, the HOMOs and that the extent of these changes can be fine-tuned, in a subtle way, by substituting at the meso-aryl rings of a given porphyrin.

Electronic structure of In1-xMnxAs studied by photoemission spectroscopy: Comparison with Ga1-xMnxAs

We have investigated the electronic structure of the p-type diluted magnetic semiconductor In1-xMnxAs by photoemission spectroscopy. The Mn 3d partial density of states is found to be basically similar to that of Ga1-xMnxAs. However, the impurity-band-like states near the top of the valence band have not been observed by angle-resolved photoemission spectroscopy unlike Ga1-xMnxAs. This difference would explain the difference in transport, magnetic and optical properties of In1-xMnxAs and Ga1-xMnxAs. The different electronic structures are attributed to the weaker Mn 3d-As 4p hybridization in In1-xMnxAs than in Ga1-xMnxAs.

First-principles electronic structure of the delafossites ABO(2) (A=Cu, Ag, Au; B=Al, Ga, Sc, In, Y): evolution of d(10)-d(10) interactions

While bonding between d(10) atoms and ions in molecular systems has been well studied, less attention has been paid to interactions between such seemingly closed shell species in extended inorganic solids. In this contribution, we present visualizations of the electronic structures of the delafossites ABO(2) (A = Cu, Ag, Au) with particular emphasis on the nature of d(10)-d(10) interactions in the close packed plane of the coinage metal ion. We find that on going from Cu to Ag to Au, the extent of bonding between A and A increases. However, the structures (in terms of distances) of these compounds are largely determined by the strongly ionic 13,11 0 interaction and for the larger B ions Sc, In and Y, the A atoms are sufficiently well-separated that A-A bonding is almost negligible. We also analyze some interesting differences between Ag and Au, including the larger A-O covalency of the Au. The trends in electronic structure suggest that the Ag and Au compounds are not good candidate transparent conducting oxides. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Electronic structure of early transition metal oxides, Ca1−xSrxVO3 and La1−xCaxVO3: What can we learn from photoelectron spectroscopy

Photoemission spectroscopy offers the unique possibility of mapping out the electronic structure of the occupied electron states. However, the extreme surface sensitivity of this technique ensures that only the surface and the near-surface regions of any sample are probed. An important question arises in this context—Is the electronic structure of the surface region the same as that of the bulk? We address this issue using two different series of vanadium oxides, Ca1−xSrxVO3 and La1−xCaxVO3. Our results clearly establish that the electronic structure of the surface region is drastically different from that of the bulk in both these cases. We provide a method to separate the two contributions: one arising from the near-surface region and the other representative of the bulk. This separation allows us to deduce some very unusual behaviors of the electronic structures in these systems.

Valence band electronic structure of Nd1-xYxMnO3 using X-ray absorption, photoemission and GGA plus U calculations

The electronic structures of Nd1-xYxMnO3 (x=0-0.5) were studied using X-ray absorption near-edge structure (XANES) at the Mn L-3,L-2- and O K-edge along with valence-band photoemission spectroscopy (VB-PES). The systematic increase in white-line intensity of the Mn L-3,L-2-edge with doping, suggests a decrease in the occupancy of Mn 3d orbitals. The O K-edge XANES shows a depletion of unoccupied states above the Fermi energy. The changes in the O K-edge spectra due to doping reflects an increase in the Jahn-Teller distortion. The VB-PES shows broadening of the features associated with Mn 3d and O 2p hybridized states and the shift of these features to a slightly higher binding energy in agreement with our GGA + U calculations. The system shows a net shift of the occupied and unoccupied states away from the Fermi energy with doping. The shift in theoretical site-projected density of states of x=0.5 composition with respect to x=0 suggest a subtle change from a charge transfer to Mott-Hubbard type insulator. (C) 2013 Elsevier B.V. All rights reserved.

INDUCTION OF FOLDED STRUCTURES IN DESIGNED PEPTIDES USING CONFORMATIONALLY CONSTRAINED RESIDUES

Folding into compact globular structures, with well-defined modules of secondary structure, appears to be a characteristic of long polypeptide chains, with a specific patterning of coded amino acid residues along the length of sequence. Cooperative hydrogen bond driven secondary structure formation and solvent forces, which contribute favorably to the entropy of folding, by promoting compaction of the polymeric chain, have long been discussed as major determinants of the folding process. First principles design approaches, which use non-coded amino acids, employ an alternative structure directing strategy, by using amino acid residues which exhibit a strong conformational bias for specific regions of the Ramachandran map. This overview of ongoing studies in the authors' laboratory, attempts to explore the use of conformationally restricted amino acid residues in the design of peptides with well-defined secondary structures. Short peptides composed of 20 genetically coded amino acids usually exist in solution as an ensemble of equilibrating conformations. Apolar peptide sequences, which are readily soluble in organic solvents like chloroform and methanol, facilitate formation of structures which are predominately driven by intramolecular hydrogen bond formation. The choice of sequences containing residues with a limited range of conformational choices strongly favors formation of local turn structures, stabilized by short range intramolecular hydrogen bonds. Two residue beta-turns can nucleate either helical or hairpin folding, depending on the precise conformation of the turn segment Restriction of the conformational space available to amino acid residues is easily achieved by introduction of an additional alkyl group at the C alpha carbon atom or by side chain backbone cyclization, as in proline. Studies of synthetic sequences incorporating two prototype residues alpha-aminoisobutyric acid (Aib) and D-proline (DPro) illustrate the utility of the strategy in construction of helices and hairpins. Extensions to the design of conformationally switchable sequences and structurally defined hybrid peptides containing backbone homologated residues are also surveyed.

Nature of the electronic band gap in lanthanide oxides

Accurate electronic structures of the technologically important lanthanide/rare-earth sesquioxides (Ln2O3, with Ln=La, ⋯,Lu) and CeO2 have been calculated using hybrid density functionals HSE03, HSE06, and screened exchange (sX-LDA). We find that these density functional methods describe the strongly correlated Ln f electrons as well as the recent G0W0@LDA+U results, generally yielding the correct band gaps and trends across the Ln period. For HSE, the band gap between O 2p states and lanthanide 5d states is nearly independent of the lanthanide, while the minimum gap varies as filled or empty Ln 4f states come into this gap. sX-LDA predicts the unoccupied 4f levels at higher energies, which leads to a better agreement with experiments for Sm2O 3, Eu2O3, and Yb2O3. © 2013 American Physical Society.

First-principles LDA plus U and GGA plus U study of neptunium dioxide

We have performed a systematic first-principles investigation to calculate the electronic structures, mechanical properties, and phonon-dispersion curves of NpO2. The local-density approximation+U and the generalized gradient approximation+U formalisms have been used to account for the strong on-site Coulomb repulsion among the localized Np 5f electrons. By choosing the Hubbard U parameter around 4 eV, the orbital occupancy characters of Np 5f and O 2p are in good agreement with recent experiments [A. Seibert, T. Gouder, and F. Huber, J. Nucl. Mater. 389, 470 (2009)]. Comparing to our previous study of ThO2, we note that stronger covalency exists in NpO2 due to the more localization behavior of 5f electrons of Np in line with the localization-delocalization trend exhibited by the actinides series.

A full spd tight-binding treatment for electronic bands of graphitic tubes

A tight-binding (TB) treatment with the inclusion of d orbitals is applied to the electronic structures of graphitic tubes. The results show that the high angular moment bases in TB scheme are necessary to account the severe curvature effect in ultra-thin single wall carbon nanotubes, especially for properly reproducing the band edge overlap behavior in (5, 0) tube, predicted by the existing ab initio calculations. In the large diameter limit, the participation of two synnmetry-allowed d bases provides a natural replication to the recent measured electronic dispersions of valence band of graphene when the strong anisotropy due to the two-dimensional planar hexagonal sheet structure is dealt with properly. In addition, the detailed relation between the two sets of quantum numbers of screw symmetry and that of zone folding is formulated in appendix. (C) 2008 Elsevier Ltd. All rights reserved.

Structure and Electronic Properties of Saturated and Unsaturated Gallium Nitride Nanotubes

The atomic and electronic structures of saturated and unsaturated GaN nanotubes along the [001] direction with (100) lateral facets are studied using first-principles calculations. Atomic relaxation of nanotubes shows that appreciable distortion occurs in the unsaturated nanotubes. All the nanotubes considered, including saturated and unsaturated ones, exhibit semiconducting, with a direct band gap Surface states arisen from the 3-fold-coordinated N and Ga atoms at the lateral facets exist inside the bulklike band gap. When the nanotubes are saturated with hydrogen, these dangling bond bands are removed from the band gap, but the band gap decreases with increasing the wall thickness of the nanotubes.

Electronic structure of self-assembled InAs quantum disks in an axial magnetic field and two-electron quantum-disk qubit

We have studied the single-electron and two-electron vertically assembled quantum disks in an axial magnetic field using the effective mass approximation. The electron interaction is treated accurately by the direct diagonalization of the Hamiltonian matrix. We calculate the six energy levels of the single-electron quantum disks and the two lowest energy levels of the two-electron quantum disks in an axial magnetic field. The change of the magnetic field strongly modifies the electronic structures as an effective potential, leading to the splitting of the levels and the crossings between the levels. The effect of the vertical alignment on the electronic structures is discussed. It is demonstrated that the switching of the ground-state spin exists between S=0 and S=1. The energy difference DeltaE between the lowest S=0 and S=1 states is shown as a function of the axial magnetic field. It is also found that the variation of the energy difference between the lowest S=0 and S=1 states in the strong-B S=0 state is fairly linear. Our results provide a possible realization for a qubit to be fabricated by current growth techniques. (C) 2004 American Institute of Physics.

Electronic structure and optical property of semiconductor nanocrystallites

Semiconductor nanostructures show many special physical properties associated with quantum confinement effects, and have many applications in the opto-electronic and microelectronic fields. However, it is difficult to calculate their electronic states by the ordinary plane wave or linear combination of atomic orbital methods. In this paper, we review some of our works in this field, including semiconductor clusters, self-assembled quantum dots, and diluted magnetic semiconductor quantum dots. In semiconductor clusters we introduce energy bands and effective-mass Hamiltonian of wurtzite structure semiconductors, electronic structures and optical properties of spherical clusters, ellipsoidal clusters, and nanowires. In self-assembled quantum dots we introduce electronic structures and transport properties of quantum rings and quantum dots, and resonant tunneling of 3-dimensional quantum dots. In diluted magnetic semiconductor quantum dots we introduce magnetic-optical properties, and magnetic field tuning of the effective g factor in a diluted magnetic semiconductor quantum dot. (C) 2004 Elsevier B.V. All rights reserved.

Effects of Sb, N, and period on the electronic properties of GaAs/GaInNAsSb superlattices

We have calculated the bond distributions and atom positions of GaAs/GalnNAsSb superlattices using Keating's semiempirical valence force field (VFF) model and Monte Carlo simulation. The electronic structures of the superlattices are calculated using folded spectrum method (FSM) combined with an empirical pseudopotential (EP) proposed by Williamson et al.. The effects of N and Sb on superlattice energy levels are discussed. We find that the deterioration of the optical properties induced by N can be explained by the localization of the conduction-band states around the N atom. The electron and hole effective masses of the superlattices are calculated and compared with the effective masses of the bulk GaAs and GaInAs.

Electronic properties of GaAs/GayIn1-yNxAs1-y-xSby superlattices

Using Keating's semiempirical valence force field model and Monte Carlo simulation, we calculate the bond distributions and atom positions of GaAs/GaInNAsSb superlattices. The electronic structures of the superlattices are calculated using the folded spectrum method combined with an empirical pseudopotential proposed by Williamson The effects of N and Sb on superlattice energy levels are discussed. The deterioration of the optical properties induced by N is explained by the localization of the conduction-band states around the N atom. The electron and hole effective masses of the superlattices are calculated and compared with the effective masses of the GaAs and GaInAs.