Ab initio theory of complex electronic ground state of superconductors: II.: Antiadiabatic state—Ground state of superconductors

Based on Q, P-dependent modification of the Born-Oppenheimer approximation (BOA), the ab initio theory of complex electronic ground state of superconductors is presented. As an illustrative example, application of the theory to superconductors of a different character and to the corresponding nonsuperconducting analogues is presented. It is shown that due to electron-phonon (EP) interactions, which drive system from adiabatic into antiadiabatic state, adiabatic translation symmetry is broken and system is stabilized in antiadiabatic state at distorted geometry with respect to adiabatic equilibrium high-symmetry structure. Stabilization effect in the antiadiabatic state is due to strong dependence of the electronic motion on the instantaneous nuclear kinetic energy, i.e. on the effect that is neglected on the adiabatic level within the BOA. At distorted geometry, antiadiabatic ground state is geometrically degenerated with fluxional nuclear configurations in the phonon modes that drive system into this state. It has been shown that until the system remains in antiadiabatic state, nonadiabatic polaron-renormalized phonon interactions are zero in the well-defined k-region of reciprocal lattice. This, along with geometric degeneracy of the antiadiabatic state, enables formation of mobile bipolarons that can move over lattice as supercarriers without dissipation. Moreover, it has been shown that due to EP interactions at transition into antiadiabatic state, k-dependent gap in one-electron spectrum has been opened. Gap opening is associated with shift of the original adiabatic Hartree-Fock orbital energies and with the k-dependent change in density of states of particular band(s) at Fermi level. Corrected one-particle spectrum enables to derive thermodynamic properties in full agreement with corresponding thermodynamic properties of superconductors.Based on the complex ab initio theory, it has been shown that Fröhlich's effective attractive electron-electron interaction term represents correction to electron correlation energy at transition from adiabatic into antiadiabatic state due to EP interactions. It has been shown that increased electron correlation is a consequence of stabilization of the system in superconducting electronic ground state, but not the reason for its formation.     

The ferromagnetic and half-metallic properties of the layered organic–inorganic hybrid Fe[CH3(CH2)2PO3(H2O)]

The density-functional theory (DFT) within the full potential linearized augmented plane wave (FPLAPW) method was applied to study the layered organic–inorganic hybrid Fe[CH₃(CH₂)₂PO₃(H₂O)]. The relative stability of the ground state, the electronic band structure, the magnetic and the conducting properties were investigated. The calculations reveal that the compound has a stable ferromagnetic ground state and the spin magnetic moment per molecule is about 4.0 μ_B, which is mainly from Fe(II) ion. By analysis of the band structure, we find that the compound has half-metallic properties.     

Classical and quantum pumping in closed systems

Pumping of charge (Q) in a closed ring geometry is not quantized even in the strict adiabatic limit. The deviation form exact quantization can be related to the Thouless conductance. We use the Kubo formalism as a starting point for the calculation of both the dissipative and the adiabatic contributions to Q. As an application we bring examples for classical dissipative pumping, classical adiabatic pumping, and in particular we make an explicit calculation for quantum pumping in case of the simplest pumping device, which is a three site lattice model. We make a connection with the popular S-matrix formalism which has been used to calculate pumping in open systems.     

The ground state and EPR spectrum in monoclinic KY(WO4)2:Nd single crystal

The electron paramagnetic resonance (EPR) of Nd³⁺ ion in KY(WO₄)₂ single crystal was investigated at T=4.2 K using an X-band spectrometer. The observed resonance absorption represents the complex superposition of three spectra corresponding to neodymium isotopes with different nuclear momenta. The EPR spectrum is characterized by a strong g-factor anisotropy. The temperature dependences of the g-factor were caused by strong spin-orbit and orbit-lattice coupling. The resonance lines become broader as temperature increases due to the short spin-lattice relaxation time.     

First principles study on electronic structure of β-Ga2O3

We have studied the electronic structure of β-Ga₂O₃ using the first principles full-potential linearized augmented plane wave method. It is found that β-Ga₂O₃ has an indirect band gap with a conduction band minimum (CBM) at Γ point and a valence band maximum on the E line. The anisotropic optical properties are explained by the selection rule of the band-to-band transitions. On the other hand, the shape of the CBM is almost isotropic and, therefore, the observed electronic anisotropy in the n-type semiconducting state should not be attributed to the properties of a perfect lattice. The Burstein-Moss shift is discussed using the effect of several allowed transitions between the levels of the valence band and the CBM.     

Electronic structure and ferromagnetism of polycrystalline Zn1−xCoxO (0≤x≤0.15)

The electronic structure of polycrystalline ferromagnetic Zn_1−xCo_xO (0.05≤x≤0.15) and the oxidation state of Co in it, have been investigated. The Co-doped polycrystalline samples are synthesized by a combustion method and are ferromagnetic at room temperature. XPS and optical absorption studies show evidence for Co²⁺ ions in the tetrahedral symmetry, indicating substitution of Co²⁺ in the ZnO lattice. However, powder XRD and electron diffraction data show the presence of Co metal in the samples. This give evidence to the fact that some Co²⁺ ion are incorporated in the ZnO lattice which gives changes in the electronic structure whereas ferromagnetism comes from the Co metal impurities present in the samples.     

Light-induced ultrafast phase transitions in VO2 thin film

Vanadium dioxide shows a passive and reversible change from a monoclinic insulator phase to a metallic tetragonal rutile structure when the sample temperature is close to and over 68 °C. As a kind of functional material, VO₂ thin films deposited on fused quartz substrates were successfully prepared by the pulsed laser deposition (PLD) technique. With laser illumination at 400 nm on the obtained films, the phase transition (PT) occurred. The observed light-induced PT was as fast as the laser pulse duration of 100 fs. Using a femtosecond laser system, the relaxation processes in VO₂ were studied by optical pump-probe spectroscopy. Upon a laser excitation an instantaneous response in the transient reflectivity and transmission was observed followed by a relatively longer relaxation process. The alteration is dependent on pump power. The change in reflectance reached a maximum value at a pump pulse energy between 7 and 14 mJ/cm². The observed PT is associated with the optical interband transition in VO₂ thin film. It suggests that with a pump laser illuminating on the film, excitation from the d_θ,? - state of valence band to the unoccupied excited mixed d_θ,?-π* - state of the conduction band in the insulator phase occurs, followed by a resonant transition to an unoccupied excited mixed d_θ,?-π* - state of the metallic phase band.     

First-principles study on the electronic structure and the ferromagnetic properties of the cyano-bridged bimetallic compound Mn2(H2O)5Mo(CN)7·4H2O (α phase)

First-principles calculations have been performed to study the electronic structure and the ferromagnetic properties of the cyano-bridged bimetallic compound Mn₂(H₂O)₅Mo(CN)₇·4H₂O (α phase).The calculations were based on density-functional theory and the full potential linearized augmented plane wave method (FP-LAPW). The calculated total energies revealed that the compound has a stable ferromagnetic (FM) ground state, which is in agreement with the experiments. The electronic structure of the compound has a half-metallic behavior. The calculated magnetic moment per molecule is about 15.000 μ_B, the magnetic moment are mainly from Mo and Mn atoms with d electronic configuration. It is also found that there exists ferromagnetic interaction between low-spin Mo²⁺ and high-spin Mn³⁺ ions through the Mo-C-N-Mn linear linkages.     

Electron affinity study of adamantane on Si(1 1 1)

Recently, tetramantane, a member of diamondoid series (C_4n+6H_4n+12), has shown to exhibit negative-electron-affinity effect which has a potential use for efficient electron emitting devices. Here, we explore the electronic property of adamantane (C₁₀H₁₆), the smallest member of the series. We prepare adamantane films on Si(1 1 1) substrates and then study their electronic structure with photoemission spectroscopy. Photoelectron spectra of adamantane on Si(1 1 1) have shown a peak at low-kinetic energy which could be a generic property of diamondoids. The possibility of the negative-electron-affinity effect in adamantane is further discussed.     

Inter-state coupling and definitions of bright and dark states

Contrary to a standard definition of diabatic states (i.e., those without momentum-dependent coupling), based on the construction from adiabatic ones, we defined diabatic states as bright and dark states of a given experiment. Namely, they are defined as states providing maximum, respectively, zero value of electronic transition dipole moments projected to a given polarization vector. Second, the state from (or to) which the optical transition is performed is not from the space of investigated electronic excited state manifold, but it is chosen by the observer. It is shown, for this case, that the inter-state coupling is a general function of vibrational coordinates. The explicit dependence of the inter-state coupling on vibrational coordinates is particularly important for system with strong Stokes shift. The role of exact definitions of bright and dark states as well as the inter-state coupling is discussed with respect to the coherent structure of electronic population observed in optical spectroscopy.     

Origin of the Q 2-dependence of the DIS structure functions

We consider in detail Q ²-dependence of the DIS structure functions. Very often this dependence is claimed to be originated by the Q ²-dependence of the QCD coupling. This leads to the small-x asymptotics of the structure functions with Q ²-dependent intercepts. We demonstrate that the DGLAP parametrization α _s = α _s (Q ²) is an approximation valid in the region of large x (where 2pq can be approximated by Q ²) only, providing the factorization scale is also large. Outside this region, the DGLAP parametrization fails, so α _s should be replaced by an effective coupling which is independent of Q ² at small x. As a consequence, intercepts of the structure functions are independent of Q ² . Nevertheless, the small-x asymptotics of the structure functions explicitly depend on Q ² , even when the coupling does not depend on it. We also consider the structure functions at small Q ² and give a comment on power-Q ² corrections to the structure functions at large and small Q ² .     

First-principle study on electronic structure and magnetic properties of organic transition metal compound: Trans-tetrachloro-bis-(pyridine)-rhenium

The electronic structure and magnetic properties of the trans-tetrachloro-bis-(pyridine)-rhenium compound with the Re atom as the metallic magnetic center, were studied using the full potential linearized augmented plane wave method (FP-LAPW) within the density functional theory. The calculated total energies revealed that the compound has a stable antiferromagnetic (AFM) ground state, which is in agreement with the experiment. The band structure of the compound has a semiconductor character. The calculated magnetic moment per molecule is 3.00 μ_B, the magnetic moments are mainly from the Re atoms with a 5d³ electronic configuration. The AFM interaction between ferromagnetically coupled Re atom layers passes through the p orbitals of the Cl ligands near Re atoms.     

Rare earth ion effects on the pseudo-gap in electron-doped superconductors and possible nodeless d-wave gap

We report angle resolved photoemission (ARPES) studies on electron-doped cuprate superconductor Sm_2-xCe_xCuO₄ (x=0.14 and 0.18). A wide energy range scan shows clear “waterfall” effect at an energy scale close to 500 meV which is consistent with the value found in Nd_2-xCe_xCuO₄ (NCCO) but larger than that from hole-doped superconductors. High resolution results from both dopings show pseudo-gap effects that were observed in NCCO. However, the effects are found to be stronger than that observed in optimally doped NCCO. The overall electronic structure is well understood within a simple model in which a static order is assumed. Both ARPES and optical measurements give the coupling strengths to the Q=(π/2,π/2) (due to the order) to be about 0.1 eV, compatible with each other. The effect is strong enough to push the band near the nodal region below the Fermi energy, resulting in possible nodeless d-wave superconductivity where zero energy quasi-particle excitation is inhibited.     

Electron-phonon interaction effects on the surface states in wurtzite nitride semiconductors

A variational approach is used to study the surface states of an electron in a semi-infinite wurtzite nitride semiconductor. The surface-state energy of the electron is calculated, by taking the effects of the electron-surface optical phonon interaction and structure anisotropy into account. The numerical computation has been performed for the energies of the electronic surface states as a function of the surface potential V₀ for wurtzite GaN, AlN, and InN, respectively. The results show that the electron-phonon interaction lowers the surface state energy. It is also found that the energies of the electronic surface-state in wurtzite structures are lower than that in the zinc-blende structures by hundreds of meV for the materials calculated. The influence of e-p-interactions on the surface state of electron cannot be neglected.     

Lithium and antimony adsorbed on graphene studied by first-principles calculations

We have investigated the Sb and Sb₂ doping of graphene and the effect of Li_n (n = 2-4) atoms in detail. We find chemisorption only when we replace C with Sb and Sb₂ and distort the lattice. The additional adsorption of Li atoms changes the electronic band structure of the system.     

Interplay of soft and hard interactions in nuclear shadowing at highQ 2 and lowx

Nuclear shadowing corrections are known to be dominated by soft interactions. They grow as function of 1/x more slowly than the single scattering term, which has an essential contribution from hard interactions. Therefore, we predict that nuclear shadowing vanishes eventually at very lowx, provided thatQ ² is high and fixed. At the same time, at medium and lowQ ², nuclear shadowing grows with 1/x. Our formalism nicely explains also the recent NMC data onQ ²-dependence of the nuclear shadowing. The effect of gluon fusion is found to be of little importance for the nuclear structure function in the available range ofx. Communicated by W. Weise     

Heterogeneous magnetic and electronic states in Ca1−xLaxMnO3−δ (x⩽0.12) single crystals with electron doping

The magnetic, transport, and optical properties of electron-doped Ca_1−xLa_xMnO_3−δ single crystals with x  ?0.12 were studied. The magnetic measurements show that in single crystals with x=0$x=0$ and 0.05 the G-type AFM phase with weak FM component is realized and in crystals with x=0.10$x=0.10$ and 0.12 the G- and C-type AFM phases coexist. The C-type magnetic structure arises at less concentration of La than in polycrystalline samples as a result of oxygen vacancies being additional source of electrons. Under magnetic transitions in the G- and C-type phases, resistivity and magnetoresistance of the doped single crystals have anomalies. Optical absorption in IR range indicates formation of a charge gap in crystals with x=0.10$x=0.10$ and 0.12 at appearance of the C-AFM and monoclinic phase with orbital/charge ordering. By comparing optical and transport properties, heterogeneous electronic state and its relation with heterogeneous magnetic state are shown.     

Determination of the neutron electric form factor in the D(e,e′n)p reaction and the influence of nuclear binding

The electric form factor of the neutron G _E,n has been determined at the Mainz Microtron MAMI at the low momentum transfer Q ²= 0.15 (GeV/c)² in a measurement of the recoil polarisation ratio P _x/P_z in the quasifree reaction D(e,e′n)p. At this Q ² the influence of the nuclear binding is strong. A purely kinematical model is used to get some insight into the effect of the initial Fermi momentum distribution of the neutron. The influence of the final state interaction is determined quantitatively by a model of Arenh?vel et al.. After the corresponding corrections a value of G _E,n(0.15 (GeV/c)²) = 0.0481±0.0065_stat±0.0053_syst is obtained. Received: 12 April 1999     

Electronic structure of BN nanotubes with intrinsic defects NB and BN and isoelectronic substitutional impurities PN, AsN, SbN, InB, GaB, and AlB

The effect of intrinsic defects and isoelectronic substitutional impurities on the electronic structure of boron-nitride (BN) nanotubes is investigated using a linearized augmented cylindrical wave method and the local density functional and muffin-tin approximations for the electron potential. In this method, the electronic spectrum of a system is governed by a free movement of electrons in the interatomic space between cylindrical barriers and by a scattering of electrons from the atomic centers. Nanotubes with extended defects of substitution N_B of a boron atom by a nitrogen atom and, vice versa, nitrogen by boron B_N with one defect per one, two, and three unit cells are considered. It is shown that the presence of such defects significantly affects the band structure of the BN nanotubes. A defect band π(B, N) is formed in the optical gap, which reduces the width of the gap. The presence of impurities also affects the valence band: the widths of s, sp, and p_π bands change and the gap between s and sp bands is partially filled. A partial substitution of the N by P atoms leads to a decrease in the energy gap, to a separation of the Ds(P) band from the high-energy region of the s(B, N) band, as well as to the formation of the impurity Dπ(P) and Dπ*(P) bands, which form the valence-band top and conduction-band bottom in the doped system. The influence of partial substitution of N atoms by the As atom on the electronic structure of BN nanotubes is qualitatively similar to the case of phosphorus, but the optical gap becomes smaller. The optical gap of the BN tubule is virtually closed due to the effect of one Sb atom impurity per translational unit cell, in contrast to the weak indium-induced perturbation of the band structure of the BN nanotube. Introduction of the one In, Ga or Al atom per three unit cells of the (5, 5) BN nanotube results in 0.6 eV increase of the optical gap. The above effects can be detected by optical and photoelectron spectroscopy methods, as well as by measuring electrical properties of the pure and doped BN nanotubes. They can be used to design electronic devices based on BN nanotubes.