Substitutional doping of Cu in diamond: Mott physics with p orbitals

Discovery of superconductivity in the impurity band formed by heavy doping of boron into diamond (C:B) as well as doping of boron into silicon (Si:B) has provided a rout for the possibility of new families of superconducting materials. Motivated by the special role played by copper atoms in high temperature superconducting materials where essentially Cu d orbitals are responsible for a variety of correlation induced phases, in this paper we investigate the effect of substitutional doping of Cu into diamond. Our extensive first principle calculations based on density functional theory which are averaged over various geometries indicate the formation of a mid-gap band, which mainly arises from the t _{2 g} and 4p states of Cu. For impurity concentrations of more than ~1%, the effect of 2p bands of neighboring carbon atoms can be ignored. Based on our detailed analysis, we suggest a two band model for the mid-gap states consisting of a quarter-filled hole like t _{2 g} band, and a half-filled band of 4p states. Increasing the concentration of the Cu impurity beyond ~5%, completely closes the spectral gap of the host diamond.     

The photoelectron spectra of the halomethanes

The photoelectron bands associated with ionization from the formally non-bonding p orbitals of the halogen atoms in the halomethanes have been interpreted in terms of a pseudo one-electron hamiltonian. Account has been taken of interactions between the halogen atoms, of interactions between the halogen p orbitals and the σ-bonding orbitals, and of spin-orbit coupling. This model leads to a systematic assignment of all the bands of the chloro and bromomethanes, and gives a satisfactory account of the spin-orbit splittings in the bromomethanes.     

Co-existing coupling schemes at high spin in 166Hf

The nucleus ¹⁶⁶Hf has been populated by the reaction ⁹⁶Zr(⁷⁴Ge,4n) using a beam energy of 310MeV. γ-rays were detected with the EUROBALL III detector array. Fourteen new normal-deformed rotational bands, of which six form coupled pairs, have been observed in ¹⁶⁶Hf. Four previously known bands have been extended to considerably higher spin, and configurations of the new bands are proposed. Two different bands have been assigned configurations involving the same orbitals at high spin. The two coupling schemes, deformation and rotation alignment, are discussed in connection with this new observation, which calls for a formulation of co-existing coupling schemes in six-quasiparticle structures involving the same orbitals at high spin.     

Two-photon-excited luminescence spectra in diamond nanocrystals

Two-photon-excited luminescence (TEL) spectra have been recorded in the blue (400–500 nm) and near-ultraviolet (300–400 nm) ranges for diamond particles with 4 nm average size, which were obtained by detonation synthesis from explosives. The observed TEL bands are attributed, by comparing the obtained spectra with the impurity luminescence spectra in large diamond crystals, to N2 and N3 defects associated with the presence of nitrogen impurities in diamond. The TEL spectra presented are found to have certain distinguishing features: short-wavelength shift of the maximum and changes in the shape and width of the spectral bands for ultradispersed diamond compared with the spectrum in bulk crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 1110–1112 (June 1999)     

New excited superdeformed bands in heavy Pb nuclei: Clue for an octupole softness near the N = 118 gap at large deformation

We report the identification of six new superdeformed (SD) bands in ^197,198Pb observed with the EUROBALL IV spectrometer. The results are interpreted in the framework of cranked Hartree-Fock calculations with approximate projection on the particle number by means of the Lipkin-Nogami method. A mixing between quasi-particle excitations and an octupole vibration is suggested in the two SD isotopes. We have estimated the ordering of the neutron valence orbitals and confirm indirectly a N = 118 SD gap. Received: 20 December 2000 / Accepted: 24 January 2001     

Optical spectroscopy of the surface of nanoporous diamond films

We have studied the IR absorption spectra of samples of porous ultrananocrystalline diamond (UNC diamond) obtained by selective etching of the sp ² phase in UNC diamond films. We show that the surface of porous UNC diamond is polyfunctional. We have studied the behavior of surface hydride, carbonyl, carboxyl, and hydroxyl groups as a function of annealing temperature in air and the time kept under normal conditions for UNC diamond films previously oxidized at 430°C–450°C. In the range from a few minutes to a few months, we studied the kinetics for establishment of the steady state for the functional adsorbed layer on the diamond surface under normal conditions. The observed growth in the intensity of the transmission bands due to hydride (CH _x ) and other hydrogen-containing functional groups is explained by dissociation of water molecules on the surface of the UNC diamond films.     

Electron pairs,localized orbitals and electron correlation

Presuming zeroth-order electronic wavefunctions generated from localized SCF or FORS molecular orbitals, the correlation energy is expressed as a bilinear form in terms of the pair populations of these orbitals and the projections of a correlation operator onto these orbitals. The latter are determined by fitting the correlation energies of large sets of organic molecules, which are reproduced with a mean absolute deviation of 1–3 kcal mol^?1. The resulting formula provides a ‘back-of-the-envelope’ method for estimating correlation energies and furnishes an analysis of these energies in terms of physical concepts and chemical structure. It Predicts the correlation energy of diamond (per carbon atom) to within 6 kcal mol^?1.     

A simple model for doublet bands in doubly odd nuclei

Nuclear structure of doublet bands in doubly odd nuclei with mass A ∼ 130 is investigated within the framework of a simple model where the even-even core couples with a neutron and a proton in intruder orbitals through a quadrupole-quadrupole interaction. The model reproduces quite well the energy levels of doublet bands and electromagnetic transitions. The staggering of the ratios B(M1;I → I - 1)/B(E2;I → I - 2) of the yrast bands turns out to be described by the chopsticks-like motion of two angular momenta of the unpaired neutron and the unpaired proton when they are weakly coupled with the core.-1 An erratum to this article is available at .     

An ab initio analysis of electronic states associated with a silicon vacancy in cubic symmetry

The electronic orbitals localized in the vicinity of a vacancy in a silicon crystal are calculated by an ab initio method based on the density functional theory and analyzed in association with the elastic softening observed by the recent ultrasonic experiments, especially focused on an estimate of the electric quadrupole moments. The localized orbitals due to the existence of a vacancy show largely extended properties and the quadrupole moments calculated from the orbitals indicate the strong dependence on cell sizes up to 511 atoms in the basic cell. Asymptotic values of the quadrupole moments in the limit of large size are obtained by an extrapolating method. It is shown that the quadrupole moments are enhanced due to the extension of the orbitals and the ratio of the quadrupole moments of Γ₅ and Γ₃ symmetries agrees well with the value deduced from the experimental results.     

Coulomb correlation effects in LaFeAsO: An LDA + DMFT(QMC) study

Effects of Coulomb correlation on the LaFeAsO electronic structure are investigated by the LDA + DMFT(QMC) method (combination of the local density approximation with the dynamic mean-field theory; impurity solver is a quantum Monte Carlo algorithm). The calculation results show that LaFeAsO is in the regime of intermediate correlation strength with a significant part of the spectral density moved from the Fermi energy to the Hubbard bands and far from the edge of the metal-insulator transition. Correlations affect iron d-orbitals differently. The t _2g states (xz, yz and x ² − y ² orbitals) have a higher energy due to crystal field splitting and are nearly half-filled. Their spectral functions have a pseudogap with the Fermi level position on the higher subband slope. The lower energy e _g set (xy and 3z ² − r ² orbitals) have occupancies significantly larger than 1/2 with typically metallic spectral functions. The article is published in the original.     

A new approach to bonding in transition metal clusters

The idea that the molecular orbitals of a cluster of atoms can be usefully classified according to their nodal structure, so that the energy increases with the number of nodes, is quantified and shown to apply in its usual form only to molecular orbitals constructed from atomic σ orbitals. The method is extended to deal with atomic π and δ orbitals by the use of vector and tensor surface harmonics respectively. In all cases the orbitals can be classified approximately in terms of angular momentum quantum numbers l and m, but in the π and δ cases there are two orbitals, with different parity, for each lm, and the energy is determined primarily by the parity. The method provides a classification scheme and an approximate energy ordering which does not depend on any point-group symmetry that the cluster may have, and therefore provides a useful framework for discussion of the bonding in cluster compounds such as the boron hydrides and the transition metal cluster carbonyls.     

Model construction and pairing symmetry for the iron-based oxypnictides

PC-19-INV: In order to clarify the mechanism of superconductivity in the iron-based compound recently discovered by Hosono’s group, we have first constructed a tight-binding model in terms of the maximally localized Wannier orbitals from a first-principles electronic structure calculation. The model has turned out to involve all the five Fe 3d bands. This is used to calculate the spin and charge susceptibilities with the five-band random-phase approximation, which are then plugged into the linearised Eliashberg equation. For a doped system we obtain an unconventional s-wave pairing with sign-reversing gap functions. To be more precise, the gap function is a 5×5 matrix, for which the diagonal elements mainly comprise d_x²-y² and d_yz,d_xz orbital components. The strong dependence of the gap between different orbitals may be observed experimentally.     

Electronic structure of heavy-metal azides

Calculations of the electronic crystal structure in the basis of pseudoatomic orbitals are used to investigate major heavy-metal azides AgN ₃ and TlN ₃. Special features and composition of the energy bands are analyzed for two cases: with allowance for spin-orbit interaction and without it. The chemical bond structure determined by the electron-density distribution is also examined.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 84–88, October, 2004.     

Ultrahigh Spin Structures in 157,158,159Er

Rotational structures at ultrahigh spin in ^157,158,159 Er have been investigated with the configuration-dependent cranked Nilsson-Strutinsky approach. Configurations of observed bands are assigned and the corresponding deformations are given theoretically. The calculations suggest that one of ultrahigh spin bands in ^158 Er is triaxial highly deformed and the other is normal-deformed, while both ultrahigh spin bands in ^157Er are suggested to be triaxial highly deformed. The possible ultrahigh spin bands in ^159Er are predicted to be triaxial highly deformed and have shape coexistence in the same configuration. The configurations with two neutron holes in the Nose = 4 orbitals and two neutron holes in the h11/2 orbitals in ^159Er are favoured for ultrahigh spin states but unfavoured for band termination, which is similar to ultrahigh spin bands in ^157,15SEr.     

Ba0.5Sr0.5TiO3电子结构和光学性质的第一性原理研究

利用第一性原理研究了Ba_0.5Sr_0.5TiO₃的能带结构和光学性质.结果表明,导带和价带都来源于钛原子3d轨道和氧原子2p轨道的杂化.导带主要由钛原子的3d轨道贡献,价带主要由氧原子的2p轨道贡献.吸收系数为10⁵ cm^-1量级,且吸收主要集中在低能区.折射率为n（0）=2.1,结果与实验符合. 关键词： 第一性原理 能带结构 光学性质     

First-principles calculations of the optical band-gaps of ZnxCd1−xO alloys

Using first-principles calculations, we investigated the structural and electronic properties of two binaries: ZnO in wurtzite structure and CdO in wurtzite and rock-salt structures. In addition several compositions with various ordered structures of Zn_xCd_1−xO alloys were studied within the theory of order–disorder transformation. The full potential linearized augmented plane wave method was used and the d orbitals of Zn and Cd were included in the valence bands. In this investigation of alloying ZnO with CdO, the fundamental band-gap of the alloys is shown to be direct and to decrease versus the Cd composition.     

The genesis of energy bands formed by sublattice states in alkaline-earth metal oxides and sulfides

The self-consistent electron energy band spectra of crystals and charged sublattices of alkaline-earth metal oxides and sulfides are calculated in the framework of the density functional theory within the pseudopotential approximation in the basis set of localized orbitals. The charge states of sublattices (such as neutral sublattices, empty metal sublattices, and doubly charged anion sublattices) are analyzed with due regard for the electrical neutrality of the crystal. It is demonstrated that the valence bands of the studied crystals are very similar to the valence bands of the doubly charged anion sublattices. The distributions of the valence electron densities of the crystals are virtually identical to those of the anion sublattices. The lower conduction bands of the crystals and doubly charged anion sublattices also almost coincide with each other for MgO and MgS but differ substantially for CaO and CaS. This is associated with the difference between the contributions from the anions and cations to the conduction band of the crystals. It is found that these contributions depend on the relative energy positions of p and d unoccupied states.

     

The method of increments—a wavefunction-based ab initio correlation method for solids

An overview of wavefunction-based correlation methods generalised for the application to solids is presented. Those methods based on a preceding Hartree–Fock treatment explicitly calculate the many-body wavefunction in contrast to the density-functional theory which relies on the ground-state density of the system. This review focus on the so-called method of increments where the correlation energy of the solid is expanded in terms of localised orbitals or of a group of localised orbitals. The method of increments is applied to a great variety of materials, from covalent semiconductors to ionic insulators, from large band-gap materials like diamond to the half-metal α$\alpha$-tin, from large molecules like fullerenes over polymers, graphite to three-dimensional solids. Rare-gas crystals where the binding is van der Waals like are treated as well as solid mercury, where the metallic binding is entirely due to correlation. Strongly correlated systems are examined and the correlation driven metal–insulator transition is described at an ab initio level.     

Particle-Number Conserving Analysis for High K Multi-Quasiparticle Bands in Odd-A Deformed Nuclei 173,175Hf

Using the Particle-number Conserving (PNC) method for treating the cranked shell model, the high K multi-quasiparticle bands in odd-A deformed nuclei ^173,175Hf are analyzed, including the variation with rotational frequency of the moment of inertia, angular momentum alignment and occupation probability of each cranked Nilsson orbital. No free parameters are involved in the PNC calculation and the experimental results are reproduced well. The microscopic mechanism of the difference between the multi-quasiparticle high K bands and the yrast bands in neighboring even-even nuclei is investigated, where the blocking effects of high j intruder orbitals near the Fermi surface play a crucial role.     

Electronic band structure of TiCl3

Energy bands for the 3d? electrons of Ti³⁺ in the high temperature structure of TiCl₃ have been calculated by the tight-binding approximation. Cubic symmetry around each Ti³⁺ is assumed and transfer between the 3p atomic orbitals of Cl^? and 3d? atomic orbitals of Ti³⁺ is considered. Two singlet bands and two doublet bands with no dispersion have been obtained. The dispersionless character is discussed by constructing Wannier functions.