Electronic structure and valence-bond band structure of cuprate superconducting materials

From ab initio calculations on various clusters representing the La2-xSrxCu(1)O(4) and Y(1)Ba(2)Cu(3)O(7) classes of high-temperature superconductors, it is shown that (i) all copper sites have a Cu(II)(d(9))oxidation state with one unpaired spin that is coupled antiferromagnetically to the spins of adjacent Cu(II) sites; (ii) oxidation beyond the cupric (Cu(II)) state leads not to Cu(III) but rather to oxidized oxygen atoms, with an oxygen ppi hole bridging two Cu(II) sites; (iii) the oxygen ppihole at these oxidized sites is ferromagnetically coupled to the adjacent Cu(II)d electrons despite the fact that this is opposed by the direct dd exchange; and (iv) the hopping of these oxygen ppi holes (in CuO sheets or chains) from site to site is responsible for the conductivity in these systems (N-electron band structures are reported for the migration of these localized charges).     

Direct Observation and Analysis of CuO2 Shear Defects in La2-xSrxCuO4

Direct observations of CuO(2) sheet defect structures in superconducting La(2-x)Sr(x)CuO(4), with x in the range 0.05 crystallographic directions, by a pure shear mechanism along the edge of the octahedral copper-oxygen units. The line defects are partial screw dislocations, with characteristic displacement vectors of the type <(a/2), 0, (c/6)>, bounding the stacking faults. The existence of this type of defect demonstrates that there is an oxygen deficiency within the CuO(2) layers. However, unlike the open ReO(3) type-related structures, the packing density of the K(2)NiF(4) structure necessarily requires that anion defects be accompanied by the loss of cations of the A type (lanthanum, strontium). Under identical synthesis conditions, no defects are observed in the parent compound La(2)CuO(4).     

The magnon pairing mechanism of superconductivity in cuprate ceramics

The magnon pairing mechanism is derived to explain the high-temperature superconductivity of both the La2-xSrxCu(1)O(4) and Y(1)Ba(2)Cu(3)O(7) systems. Critical features include (i) a one- or two-dimensional lattice of linear Cu-O-Cu bonds that contribute to large antiferromagnetic (superexchange) coupling of the Cu(II)(d(9)) orbitals; (ii) holes in the oxygen ppi bands [rather than Cu(III)(d(8))] leading to high mobility hole conduction; and (iii) strong ferromagnetic coupling between oxygen ppi holes and adjacent Cu(II)(d(9)) electrons. The ferromagnetic coupling of the conduction electrons with copper d spins induces the attractive interaction responsible for the superconductivity, leading to triplet-coupled pairs called "tripgems." The disordered Heisenberg lattice of antiferromagnetically coupled copper d spins serves a role analogous to the phonons in a conventional system. This leads to a maximum transition temperature of about 200 K. For La(1.85)Sr(0.15)Cu(1)O(4), the energy gap is in excellent agreement with experiment. For Y(1)Ba(2)Cu(3)O(7), we find that both the CuO sheets and the CuO chains can contribute to the supercurrent.     

A structural probe of the doped holes in cuprate superconductors

An unresolved issue concerning cuprate superconductors is whether the distribution of carriers in the CuO2 plane is uniform or inhomogeneous. Because the carriers comprise a small fraction of the total charge density and may be rapidly fluctuating, modulations are difficult to detect directly. We demonstrate that in anomalous x-ray scattering at the oxygen K edge of the cuprates, the contribution of carriers to the scattering amplitude is selectively magnified 82 times. This enhances diffraction from the doped holes by more than 10(3), permitting direct structural analysis of the superconducting ground state. Scattering from thin films of La2CuO4+delta (superconducting transition temperature = 39 K) at temperature = 50 +/- 5 kelvin on the reciprocal space intervals (0,0,0.21) --> (0,0,1.21) and (0,0,0.6) --> (0.3,0,0.6) shows a rounding of the carrier density near the substrate suggestive of a depletion zone or similar effect. The structure factor for off-specular scattering was less than 3 x 10(-7) electrons, suggesting an absence of in-plane hole ordering in this material.     

c-axis electrodynamics as evidence for the interlayer theory of high-temperature superconductivity

In the interlayer theory of high-temperature superconductivity, the interlayer pair tunneling energy (similar to the Josephson or Lawrence-Doniach energy) is the motivation for superconductivity. This connection requires two experimentally verifiable identities: the coherent normal-state conductance must be smaller than the "Josephson" coupling energy, and the Josephson coupling energy must be equal to the condensation energy of the superconductor. The first condition is well satisfied in the only case that is relevant, (La, Sr)2CuO4, but the second condition has been questioned. It is satisfied for all dopings in (La,Sr)2CuO4 and also in optimally doped Hg(Ba)2CuO5, which was measured recently, but seems to be strongly violated in measurements on single crystals of Tl2Ba2CuO6.     

Precipitate formation in the strontium-phosphate system

Study of the precipitation process in the aqueous Sr(OH)(2)-H(3)PO(4) system, in order to elucidate the phase transformations and the nature of the final solid phases, shows that over much of the range of compositions studied the initial precipitate is poorly crystalline; the x-ray pattern resembles that of strontium hydroxyapatite but has a strontium: phosphorus molar ratio close to 1.3. Within 1 hour the initial precipitate changes to a stable crystalline phase (or phases), with corresponding change, either up or down, in the strontium: phosphorus ratio. At high ratios of Sr(OH)(2) to H(2)PO(4) the initial precipitate is Sr(3)(PO(4))(2)-4H(2)O, which then converts to a phase having the x-ray diffraction pattern of strontium hydroxyapatite, but having a strontium: phosphorus ratio that depends somewhat on the initial ratio of Sr(OH)(2) to H(3)PO(4) used in the precipitation.     

Large groundwater strontium flux to the oceans from the Bengal Basin and the marine strontium isotope record

Strontium concentration and isotopic data for subsurface flowing groundwaters of the Ganges-Brahmaputra (G-B) delta in the Bengal Basin demonstrate that this is a potentially significant source of strontium to the oceans, equal in magnitude to the dissolved strontium concentration carried to the oceans by the G-B river waters. The strontium concentrations of groundwaters are higher by a factor of about 10 than typical G-B river waters and they have similar 87Sr/86Sr ratio to the river waters. These new data suggest that the present contribution of the G-B system to the rise in 87Sr/86Sr ratio in seawater is higher by at least a factor of 2 to 5 than the average over the past 40 million years.     

Imaging doped holes in a cuprate superconductor with high-resolution Compton scattering

The high-temperature superconducting cuprate La(2-x)Sr(x)CuO(4) (LSCO) shows several phases ranging from antiferromagnetic insulator to metal with increasing hole doping. To understand how the nature of the hole state evolves with doping, we have carried out high-resolution Compton scattering measurements at room temperature together with first-principles electronic structure computations on a series of LSCO single crystals in which the hole doping level varies from the underdoped (UD) to the overdoped (OD) regime. Holes in the UD system are found to primarily populate the O 2p(x)/p(y) orbitals. In contrast, the character of holes in the OD system is very different in that these holes mostly enter Cu d orbitals. High-resolution Compton scattering provides a bulk-sensitive method for imaging the orbital character of dopants in complex materials.     

Tuning High-Tc Superconductors via Multistage Intercalation

Multistage intercalation has been used to tune the interaction between adjacent blocks of CuO(2) sheets in the bigh-T(c) (high superconducting transition temperature) superconductor Bi(2)Sr(2)CaCu(2)Ox. As revealed by atomic-resolution transmission electron microscopy images, foreign iodine atoms are intercalated into every nth BiO bilayer of the host crystal, resulting in structures of stoichiometry IBi2nSr2nCanCu2nOx with stage index n up to 4. An expansion of 3.6 angstroms for each intercalated BiO bilayer decouples the CuO(2) sheets in adjacent blocks. A comparison of the superconducting transition temperatures of the pristine host material and intercalated compounds of different stages suggests that the coupling between each pair of adjacent blocks contributes approximately 5 K to T(c) in Bi(2)Sr(2)CaCu(2)Ox.     

Suppression of collisional shifts in a strongly interacting lattice clock

Optical lattice clocks with extremely stable frequency are possible when many atoms are interrogated simultaneously, but this precision may come at the cost of systematic inaccuracy resulting from atomic interactions. Density-dependent frequency shifts can occur even in a clock that uses fermionic atoms if they are subject to inhomogeneous optical excitation. However, sufficiently strong interactions can suppress collisional shifts in lattice sites containing more than one atom. We demonstrated the effectiveness of this approach with a strontium lattice clock by reducing both the collisional frequency shift and its uncertainty to the level of 10(-17). This result eliminates the compromise between precision and accuracy in a many-particle system; both will continue to improve as the number of particles increases.     

X-ray diffraction and computation yield the structure of alkanethiols on gold(111)

The structure of self-assembled monolayers (SAMs) of long-chain alkyl sulfides on gold(111) has been resolved by density functional theory-based molecular dynamics simulations and grazing incidence x-ray diffraction for hexanethiol and methylthiol. The analysis of molecular dynamics trajectories and the relative energies of possible SAM structures suggest a competition between SAM ordering, driven by the lateral van der Waals interaction between alkyl chains, and disordering of interfacial Au atoms, driven by the sulfur-gold interaction. We found that the sulfur atoms of the molecules bind at two distinct surface sites, and that the first gold surface layer contains gold atom vacancies (which are partially redistributed over different sites) as well as gold adatoms that are laterally bound to two sulfur atoms.     

Superconducting pair correlations in an amorphous insulating nanohoneycomb film

The Cooper pairing mechanism that binds single electrons to form pairs in metals allows electrons to circumvent the exclusion principle and condense into a single superconducting or zero-resistance state. We present results from an amorphous bismuth film system patterned with a nanohoneycomb array of holes, which undergoes a thickness-tuned insulator-superconductor transition. The insulating films exhibit activated resistances and magnetoresistance oscillations dictated by the superconducting flux quantum h/2e. This 2e period is direct evidence indicating that Cooper pairing is also responsible for electrically insulating behavior.     

Manipulating Chlorine Atom Bonding on the Si(100)-(2 x 1) Surface with the STM

Chlorine atoms strongly chemisorbed at dangling bond sites on the Si(100)-(2 x 1) surface are observed by scanning tunneling microscopy (STM) to hop between adjacent sites. The origin of this behavior is suggested to be an interaction between the field of the probe tip and the dipole moment of the silicon-chlorine bond. Chlorine atom migration is shown to be facilitated by the presence of a metastable chlorine bridge-bonded minimum. The STM probe was used to excite single chlorine atoms into this bridging configuration, resulting in a local population inversion. Selective application of voltage pulses between the probe tip and the surface rearranged the local bonding and induced transformations between different types of chlorine sites. In this manner, adsorbed species can be dissected and their composition and structure directly probed.     

Theoretical evidence for a c60 "window" mechanism

On the basis of semiempirical and high-level ab initio calculations, theoretical evidence is presented of a "window" mechanism operable on the surface of C(60) and other fullerenes. Through this mechanism, large holes may be formed in fullerenes excited to their triplet state, openings through which atoms and small molecules can pass. This work provides a theoretical foundation for experiments that have prepared endohedral noble gas compounds of C(60) under thermal excitation. A method is proposed that could increase the efficiency of the process of noble gas insertion into C(60) and provide a more general means to create endohedral fullerene compounds.     

An intrinsic bond-centered electronic glass with unidirectional domains in underdoped cuprates

Removing electrons from the CuO2 plane of cuprates alters the electronic correlations sufficiently to produce high-temperature superconductivity. Associated with these changes are spectral-weight transfers from the high-energy states of the insulator to low energies. In theory, these should be detectable as an imbalance between the tunneling rate for electron injection and extraction-a tunneling asymmetry. We introduce atomic-resolution tunneling-asymmetry imaging, finding virtually identical phenomena in two lightly hole-doped cuprates: Ca(1.88)Na(0.12)CuO(2)Cl2 and Bi2Sr2Dy(0.2)Ca(0.8)Cu2O(8+delta). Intense spatial variations in tunneling asymmetry occur primarily at the planar oxygen sites; their spatial arrangement forms a Cu-O-Cu bond-centered electronic pattern without long-range order but with 4a(0)-wide unidirectional electronic domains dispersed throughout (a(0): the Cu-O-Cu distance). The emerging picture is then of a partial hole localization within an intrinsic electronic glass evolving, at higher hole densities, into complete delocalization and highest-temperature superconductivity.     

Himalayan tectonics, weathering processes, and the strontium isotope record in marine limestones

The time evolution of the isotopic composition of seawater strontium (the ratio of strontium-87 to strontium-86) over the last 500 million years has the form of an asymmetric trough. The values are highest in the Cambrian and Recent (0.7091) and lowest in the Jurassic (0.7067). Superimposed on this trend are a number of smaller oscillations. Consideration of the geochemical cycle of strontium and the dynamics of weathering shows that only Himalayan-style continental collisions can influence the isotope ratio on the scale observed. The contemporary Himalayan orogeny is by far the largest since the late Precambrian Pan-African event that produced the high in the Cambrian.     

Orbital reconstruction and covalent bonding at an oxide interface

Orbital reconstructions and covalent bonding must be considered as important factors in the rational design of oxide heterostructures with engineered physical properties. We have investigated the interface between high-temperature superconducting (Y,Ca)Ba(2)Cu3O7 and metallic La(0.67)Ca(0.33)MnO3 by resonant x-ray spectroscopy. A charge of about -0.2 electron is transferred from Mn to Cu ions across the interface and induces a major reconstruction of the orbital occupation and orbital symmetry in the interfacial CuO2 layers. In particular, the Cu d(3z(2)-r(2)) orbital, which is fully occupied and electronically inactive in the bulk, is partially occupied at the interface. Supported by exact-diagonalization calculations, these data indicate the formation of a strong chemical bond between Cu and Mn atoms across the interface. Orbital reconstructions and associated covalent bonding are thus important factors in determining the physical properties of oxide heterostructures.     

Sr lattice clock at 1 x 10(-16) fractional uncertainty by remote optical evaluation with a Ca clock

Optical atomic clocks promise timekeeping at the highest precision and accuracy, owing to their high operating frequencies. Rigorous evaluations of these clocks require direct comparisons between them. We have realized a high-performance remote comparison of optical clocks over kilometer-scale urban distances, a key step for development, dissemination, and application of these optical standards. Through this remote comparison and a proper design of lattice-confined neutral atoms for clock operation, we evaluate the uncertainty of a strontium (Sr) optical lattice clock at the 1 x 10(-16) fractional level, surpassing the current best evaluations of cesium (Cs) primary standards. We also report on the observation of density-dependent effects in the spin-polarized fermionic sample and discuss the current limiting effect of blackbody radiation-induced frequency shifts.     

In-Plane Structure of the Liquid-Vapor Interface of an Alloy: A Grazing Incidence X-ray Diffraction Study of Bismuth:Gallium

The liquid-vapor interface of a bismuth-gallium mixture (0.2 percent bismuth and 99.8 percent gallium) at 36 degrees C has been studied by grazing incidence x-ray diffraction. The data show, in agreement with thermodynamic arguments, that bismuth is heavily concentrated in the liquid-vapor interface. The x-ray diffraction data are interpreted with the assistance of a simple model that represents the interface as a partial monolayer of bismuth. This analysis leads to the conclusion that the bismuth concentration in the interface is about 80 percent, that there is no significant mixing of gallium and bismuth in the interface, and that the structure function of the interfacial bismuth is like that of supercooled bulk liquid bismuth.     

Magnetic flux transport on the sun

Although most of the magnetic flux observed on the sun originates in the low-latitude sunspot belts, this flux is gradually dispersed over a much wider range of latitudes by supergranular convective motions and meridional circulation. Numerical simulations show how these transport processes interact over the 11-year sunspot cycle to produce a strong "topknot" polar field, whose existence near sunspot minimum is suggested by the observed strength of the interplanetary magnetic field and by the observed areal extent of polar coronal holes. The required rates of diffusion and flow are consistent with the decay rates of active regions and with the rotational properties of the large-scale solar magnetic field.