Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABOs (A=La or rare-earth ion, B=trivalent transition metalion). Systematics in the core levels and in the valence bands in the series of LaBOa compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNil_x Coxes, LaNix_x FexO8 and LaFel_x Coxes show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites.

Systematic Organic UV Photoelectron Spectroscopy

Photoelectron spectroscopy (PES) provides valuable information on the ionization energies of atoms and molecules. The ionization energy (IE) is given by the relation.hv = IE + T where hv is t h e energy of the radiation and T i s the kinetic energy of the electron. The IEs are directly related to the orbital energies (Koopmans' theorem). By employing UV radiation (HeI. 21.2 eV. or HeII. 40.8 eV). extensive data on the ionization of valence electrons in organic molecules have been obtained in recent years. These studies of UV photoelectron spectroscopy. originated by Turner, have provided a direct probe into the energy levels of organic molecules. Molecular orbital calculations of various degrees of sophistication are generally employed to make assignments of the PES bands. Analysis of the vibrational structure of PES bands has not only provided structural information on the molecular ions, but has also been of value in band assignments. Dewar and co-workers [1, 2) presented summaries of available PES data on organic molecules in 1969 and 1970. Turner et al. [3] published a handbook of Hel spectra of organic molecules in 1970. Since then, a few books [4-7] discussing the principles and applications of UV photoelectron spectroscopy have appeared of which special mention should be made of the recent article by Heilbronner and Maier [7]. There has, however, been no comprehensive review of the vast amount of data on the UV-PES of organic molecules published in the literature since 1970.

A study on boundary-layer transition induced by free-stream turbulence

Boundary-layer transition at different free-stream turbulence levels has been investigated using the particle-image velocimetry technique. The measurements show organized positive and negative fluctuations of the streamwise fluctuating velocity component, which resemble the forward and backward jet-like structures reported in the direct numerical simulation of bypass transition. These fluctuations are associated with unsteady streaky structures. Large inclined high shear-layer regions are also observed and the organized negative fluctuations are found to appear consistently with these inclined shear layers, along with highly inflectional instantaneous streamwise velocity profiles. These inflectional velocity profiles are similar to those in the ribbon-induced boundary-layer transition. An oscillating-inclined shear layer appears to be the turbulent spot-precursor. The measurements also enabled to compare the actual turbulent spot in bypass transition with the simulated one. A proper orthogonal decomposition analysis of the fluctuating velocity field is carried out. The dominant flow structures of the organized positive and negative fluctuations are captured by the first few eigenfunction modes carrying most of the fluctuating energy. The similarity in the dominant eigenfunctions at different Reynolds numbers suggests that the flow prevails its structural identity even in intermittent flows. This analysis also indicates the possibility of the existence of a spatio-temporal symmetry associated with a travelling wave in the flow.

Optical and magnetic properties of the exact PPP states of biphenyl

The low-lying singlets and triplets of biphenyl are obtained exactly within the PPP model using the diagrammatic valence bond method. The energy gaps within the singlet manifold as well as the lowest singlet-triplet gap are found to be in good agreement with experimental results. The two weak absorptions between 4·1 and 4·2 eV reported experimentally are attributed to the two states lying below the optical gap that become weakly allowed on breaking electron-hole and inversion symmetries. The observed blue shift of the spectral lines, attributed to a change in dihedral angle, on going from crystalline to solution to vapour phase is also well reproduced within the PPP model. The bond orders show that the ground singlet state is benzenoidal while the dipole excited state as well as the lowest triplet state are quinonoidal and planar. Comparison with the experimental spin densities and the fine structure constants D and E in the triplet state point to slightly weaker correlations than assumed by the PPP model. The introduction of a 1-8 bond to mimic poly(paraphenylene)s gives an optical gap that is in good agreement with experiment.

QCD with dynamical Wilson fermions. II

We present results for the QCD spectrum and the matrix elements of scalar and axial-vector densities at β=6/g2=5.4, 5.5, 5.6. The lattice update was done using the hybrid Monte Carlo algorithm to include two flavors of dynamical Wilson fermions. We have explored quark masses in the range ms≤mq≤3ms. The results for the spectrum are similar to quenched simulations and mass ratios are consistent with phenomenological heavy-quark models. The results for matrix elements of the scalar density show that the contribution of sea quarks is comparable to that of the valence quarks. This has important implications for the pion-nucleon σ term.

Reactivity Of Pph3 Toward Ruiiruiiicl(O2car)4 - Syntheses, Molecular-Structures, And Spectroscopic And Electrochemical Properties Of Ruiiruiii(Oh2)Cl(Mecn)(O2car)4(Pph3)2 And Ruii2(Oh2)(Mecn)2(O2car)4(Pph3)2

By the reaction of Ru2Cl(O2CAr)4 (1) and PPh3 in MeCN-H2O the diruthenium(II,III) and diruthenium(II) compounds of the type Ru2(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 (2) and Ru2(OH2)(MeCN)2(O2CAr)4(PPh3)2 (3) were prepared and characterized by analytical, spectral, and electrochemical data (Ar is an aryl group, C6H4-p-X; X = H, OMe, Me, Cl, NO2). The molecular structure of Ru2(OH2)Cl(MeCN)(O2CC6H4-p-OMe)4(PPh3)2 was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.538 (5) angstrom, b = 15.650 (4) angstrom, c = 18.287 (7) angstrom, alpha = 101.39 (3)-degrees, beta = 105.99 (4)-degrees, gamma = 97.94 (3)-degrees, V = 3574 angstrom 3, Z = 2. The molecule is asymmetric, and the two ruthenium centers are clearly distinguishable. The Ru(III)-Ru(II), Ru(III)-(mu-OH2), and Ru(II)-(mu-OH2) distances and the Ru-(mu-OH2)-Ru angle in [{Ru(III)Cl(eta-1-O2CC6H4-p-OMe)(PPh3)}(mu-OH2)(mu-O2CC6H4-p-OMe)2{Ru(II)(MeCN)(eta-1-O2CC6H4-p-OMe)(PPh3)}] are 3.604 (1), 2.127 (8), and 2.141 (10) angstrom and 115.2 (5)-degrees, respectively. The compounds are paramagnetic and exhibit axial EPR spectra in the polycrystalline form. An intervalence transfer (IT) transition is observed in the range 900-960 nm in chloroform in these class II type trapped mixed-valence species 2. Compound 2 displays metal-centered one-electron reduction and oxidation processes near -0.4 and +0.6 V (vs SCE), respectively in CH2Cl2-TBAP. Compound 2 is unstable in solution phase and disproportionates to (mu-aquo)diruthenium(II) and (mu-oxo)diruthenium(III) complexes. The mechanistic aspects of the core conversion are discussed. The molecular structure of a diruthenium(II) compound, Ru2(OH2)(MeCN)2(O2CC6H4-p-NO2)4(PPh3)2.1.5CH2Cl2, was obtained by X-ray crystallography. The compound crystallizes in the space group P2(1)/c with a = 23.472 (6) angstrom, b = 14.303 (3) angstrom, c = 23.256 (7) angstrom, beta = 101.69 (2)-degrees, V = 7645 angstrom 3, and Z = 4. The Ru(II)-Ru(II) and two Ru(II)-(mu-OH2) distances and the Ru(II)-(mu-OH2)-Ru(II) angle in [{(PPh3)-(MeCN)(eta-1-O2CC6H4-p-NO2)Ru}2(mu-OH2)(mu-O2CC6H4-p-NO2)2] are 3.712 (1), 2.173 (9), and 2.162 (9) angstrom and 117.8 (4)-degrees, respectively. In both diruthenium(II,III) and diruthenium(II) compounds, each metal center has three facial ligands of varying pi-acidity and the aquo bridges are strongly hydrogen bonded with the eta-1-carboxylato facial ligands. The diruthenium(II) compounds are diamagnetic and exhibit characteristic H-1 NMR spectra in CDCl3. These compounds display two metal-centered one-electron oxidations near +0.3 and +1.0 V (vs SCE) in CH2Cl2-TBAP. The overall reaction between 1 and PPh3 in MeCN-H2O through the intermediacy of 2 is of the disproportionation type. The significant role of facial as well as bridging ligands in stabilizing the core structures is observed from electrochemical studies.

Some observations of tip-vortex cavitation

Cavitation has been observed in the trailing vortex system of an elliptic planform hydrofoil. A complex dependence on Reynolds number and gas content is noted at inception. Some of the observations can be related to tension effects associated with the lack of sufficiently large-sized nuclei. Inception measurements are compared with estimates of pressure in the vortex obtained from LDV measurements of velocity within the vortex. It is concluded that a complete correlation is not possible without knowledge of the fluctuating levels of pressure in tip-vortex flows. When cavitation is fully developed, the observed tip-vortex trajectory shows a surprising lack of dependence on any of the physical parameters varied, such as angle of attack, Reynolds number, cavitation number, and dissolved gas content.

Photoconductivity in β-AgI

Excitation spectra and transient and steady-state photoconductivity have been studied in undoped and 0.8-mole% Cu-doped single-crystal β-AgI between 150 and 260°K. A single peak in the spectral response was found to occur in each case, at 2.88 eV for undoped and at 2.81 eV for copper-doped specimens at 260 K, the difference being due to a decrease in band gap. The anisotropy due to polarization of incident radiation parallel or perpendicular to the c direction, which is a measure of the energy difference between the Γ9 and Γ7 levels in the valence band, was found to be 0.010 eV. Transient-photoconductivity experiments showed that the hole lifetime was 6 μ sec at 300°K, an order of magnitude larger than the electron lifetime. The hole drift mobility was found to be 12±2 cm2/ V sec at 300°K and limited by traps at a depth of 0.51±0.01 eV with concentration (3-5)×109/cm3 and capture cross section 10-11 cm2. The study of photoconductivity decay versus temperature revealed the presence of shallow hole traps at 0.14±0.02 eV with concentration greater than 1016/cm3 and capture cross section 10-19 cm2. The steady-state photoconductivity was determined by the deep hole traps at 0.51 eV, and showed the presence of shallow electron traps at a depth of 0.28 eV. The trap distribution was found to be substantially the same in pure and copper-doped specimens, indicating the monovalent substitutional role of copper. The effects of iodine annealing, cadmium doping, and heating above the transition temperature were also studied. The possible nature of the traps is discussed.

Pes study of spin-state transitions in d6 transition metal complexes and oxides

Transitions from the low-to the high-spin state in Fe2+ and Co3+ compounds have been examined by X-ray and UV photoelectron spectroscopy. It has been shown that the core-level bands in XPES, in particular the metal 3s band, as well as the valence bands, are diagnosis in the study of spin-state transitions.

Structure, dielectric, and magnetic properties of Sr2TiMnO6 ceramics

Sr2TiMnO6, a double perovskite associated with high degree of B-site cation disorder was investigated in detail for its structural, magnetic, and dielectric properties. Though x-ray powder diffraction analysis confirms its cubic structure, first order Raman scattering and infrared reflectivity spectra indicate a breaking of the local cubic symmetry. The magnetization study reveals an anomaly at 14 K owing to a ferrimagnetic/canted antiferromagneticlike ordering arising from local Mn-O-Mn clusters. Saturated M-H hysteresis loops obtained at 5 K also reflect the weak ferromagnetic exchange interactions present in the system and an approximate estimation of Mn3+/Mn4+ was done using the magnetization data for the samples sintered at different temperatures. The conductivity and dielectric behavior of this system has been investigated in a broad temperature range of 10 to 300 K. Intrinsic permittivity was obtained only below 100 K whereas giant permittivity due to conductivity and Maxwell-Wagner polarization was observed at higher temperatures. X-ray photoemission studies further confirmed the presence of mixed oxidation states of Mn and the valence band spectra analysis was carried out in detail. (C) 2010 American Institute of Physics. doi: 10.1063/1.3500369]

Chemical Shift of the X-Ray K-Absorption Edge of Cu in Some of Its Compounds, Complexes and Superconductors

Chemical shifts, ΔE, of the X-ray K-absorption edge in several compounds, complexes of copper including its superconducting oxides possessing formal oxidation states +1 and +2 have been measured. It has been shown that the chemical shift is primarily governed by the effective ionic charge on the absorbing ion and the nature of the atoms in the first coordination shell around the absorbing ion. The relation between the chemical shift, ΔE , and the effective charge q on the absorbing ion is found to be ΔE=Aq+Bq2+Cq3+Dq4 (A, B, C and D are constants). The effects of electronegativity, atomic number, oxidation state, crystal structure, the valence d-orbital electrons, etc. on the X-ray absorption chemical shift have been discussed. ©1990 The Physical Society of Japan

Approximate VB-MO schemes for excitation gaps in Hubbard models

The excitation gaps in the singlet and triplet manifolds for finite Hubbard models in one, two and three dimensions have been obtained using different approximate configuration interaction (CI) schemes, as a function of the correlation strength, by using valence bond (VB) functions constructed over the molecular orbital (MO) basis. These are compared with numerically exact results and it is found that the scheme in which all particle hole excitations below a given threshold are included is the method of choice. The excitation energies are well reproduced, in trend as well as magnitude, particularly when the threshold equals the bandwidth of the corresponding noninteracting system.

Exact eigenstates of the Pariser-Parr-Pople model for anthracene

The pi-electronic structure of anthracene is discussed by combining exact solutions of the Pariser-Parr-Pople (PPP) model and semiempirical PM3 calculations. Symmetry adaptation of the 2.8 million singlet valence-bond (VB) diagrams is explicitly demonstrated for D2h and electron-hole symmetry. Standard PPP parameters provide a comprehensive fit to one- and two-photon anthracene spectra and intensities up to the strong 1 B-1(3u)-absorption at 5.24 eV, the 10th excited state in the dense correlated spectrum, and indicate a reassignment of two-photon absorptions. The singlet-triplet gap and fine-structure constants also agree with experiment. Fully-relaxed PM3 geometries are obtained for the anthracene ground state and for singlet, triplet, and charged bipolarons. The PM3 bond lengths correlate well with PPP bond orders for the idealized structure. Single-determinantal PM3 excitation and relaxation energies for bipolarons are consistent with exact PPP results and contrast all-valence electron with pi-electron calculations. Several correlation effects are noted in the rich pi-spectra of anthracene in connection with improved PPP modeling of conjugated molecules and polymers.

Fe-57 Mössbauer and Mo K-EXAFS Investigations of MoxFe3-xO4, an Interesting Mixed-Valent Oxide System

Ferrites of the formula MoxFe3-xO4, prepared by a soft-chemistry route, show mixed valence states of both iron and molybdenum cations. Mössbauer studies show that Fe2+ and Fe3+ ions are present on both the A and B sites, giving Fe an average oxidation state between 2+ and 3+. Molybdenum is present in the 3+ and the 4+ states on the B sites. The presence of Mo in the 3+ state has been established by determining the Mo3+-O distance (2.2 Å), for the first time, by Mo K-EXAFS. The mixed valence of Fe on both the A and B sites and of Mo on the B sites is responsible for the fast electron transfer between the cations. All the Mössbauer parameters including the line width show a marked change at a composition (x ? 0.3) above which the concentration of Fe2+A increases rapidly.

Interaction of solid films of C60 and C70 with nickel

Interaction of varying coverages of Ni metal with solid films of C60 and C70 has been investigated by UV and X-ray photemission spectroscopy. The shifts in the valence bands of C60 (as well as of C70) with increasing Ni coverage accompanied by a shift of the C is level of the fullerene to lower binding energies suggest charge-transfer from the metal to the fullerene as in transition metal complexes of π-systems.