Study of solids and surfaces by photoacoustic spectroscopy

Photoacoustic spectroscopy has been employed to study the electronic spectra of a variety of solids. The systems studied include powders of intensely coloured dyes, amorphous chalcogenides and oxide gels besides polycrystalline samples of several oxide materials. Surface sensitivity of the technique has been examined by study of dye adsorption on oxide surfaces and determination of surface areas of active oxides. Acidic and basic sites on catalyst surfaces have also been estimated by this technique.

Ambidentate coordination of isonitrosoacetylacetone imines in their nickel(II) and palladium(II) complexes

Nickel(I1) and palladium(I1) complexes of the types Ni(R-IAI)(IAI'), Pd(IAI)(IAI'), and Pd(R-IAI), , where IAI and IAI' represent isonitrosoacetylacetone imine and R-IAI represents its Aralkyl derivative, have been prepared. The molar conductance, molecular weight, magnetic moment, and ir, pmr, and electronic spectra of these com- plexes have been studied. It is suggested that the isonitroso group of R-IAI coordinates through the nitrogen and that of IAI' thiough the oxygen in Ni(R-IAI)(IAI'). In Pd(R-IAI), the isonitroso groups of both ligands coordinate through nitrogen while Pd(IAI)(IAI') has a structure similar to that of Ni(R-IAI)(IAI'). The amine- exchange reactions of nickel(I1) and palladium(I1) complexes are discussed and compared on the basis of their structures.

Optical and magnetic resonance studies of the interaction of metallo tetraphenylporphyrins with nitrobenzofuroxan

Metallo tetraphenylporphyrins form I : I molecular complexes with 4,6-dinitrobenzofuroxan. The molecular association is described in terms of T-n. interaction with porphyrins functioning as donors. The association constants and thermodynamic parameters have been evaluated using optical absorption and 'H nmr spectral methods. Based on the binding constants, the donor ability of various metalloporphyrins can be arranged in the following order: Pd(I1) > Co(I1) > Cu(I1) > Ni(I1) - VO(1V) - 2H > Zn(l1). Electron paramagnetic resonance studies of the complexes reveal that the IT-complexation results in changes in the electronic structure of the central metal ions which are reflected in the changes in the M-N 5 bonding. The dipolar contribution to the acceptor proton chemical shifts in the CoTPP complex has been partitioned from ring current contributions using the shifts observed in the ZnTPP complex. The shifts, along with the line broadening ratios observed for the CoTPP complex, are used to arrive at the possible solution structures of the complexes.

Metal-insulator transition of naxwo3 studied by angle-resolved photoemission spectroscopy

The electronic structure of sodium tungsten bronzes NaxWO3 is investigated by high-resolution angle-resolved photoemission spectroscopy (ARPES). The ARPES spectra measured in both insulating and metallic phases of NaxWO3 reveals the origin of metal-insulator transition (MIT) in sodium tungsten bronze system. It is found that in insulating NaxWO3 the states near the Fermi level (E-F) are localized due to the strong disorder caused by the random distribution of Na+ ions in WO3 lattice. Due to the presence of disorder and long-range Coulomb interaction of conduction electrons, a soft Coulomb gap arises, where the density of states vanishes exactly at E-F. In the metallic regime the states near E-F are populated and the Fermi level shifts upward rigidly with increasing electron doping (x). Volume of electron-like Fermi surface (FS) at the Gamma(X) point of the Brillouin zone gradually increases with increasing Na concentration due to W 5d t(2g) band filling. A rigid shift of the Fermi energy is found to give a qualitatively good description of the Fermi surface evolution. As we move from bulk-sensitive to more surface sensitive photon energy, we found the emergence of Fermi surfaces at X(M) and M(R) point similar to the one at the Gamma(X) point in the metallic regime, suggesting that the reconstruction of surface was due to rotation/deformation of WO6 octahedra.

Field Emission Properties of Carbon Nanotube Arrays with Defects and Impurities

It has been found experimentally that the results related to the collective field emission performance of carbon nanotube (CNT) arrays show variability. The emission performance depends on the electronic structure of CNTs (especially their tips). Due to limitations in the synthesis process, production of highly pure and defect free CNTs is very difficult. The presence of defects and impurities affects the electronic structure of CNTs. Therefore, it is essential to analyze the effect of defects on the electronic structure, and hence, the field emission current. In this paper, we develop a modeling approach for evaluating the effect of defects and impurities on the overall field emission performance of a CNT array. We employ a concept of effective stiffness degradation for segments of CNTs, which is due to structural defects. Then, we incorporate the vacancy defects and charge impurity effects in our Green's function based approach. Simulation results indicate decrease in average current due to the presence of such defects and impurities.

Synthesis, Structure, and Properties of Boron- and Nitrogen-Doped Graphene

Boron- and nitrogen-doped graphenes are are prepared by the arc discharge between carbon electrodes or by the transformation of nanodiamond under appropriate atmospheres. Using a combination of experiment and theories based on first principles, systematic changes in the carrier-concentration and electronic structure of the doped graphenes are demonstrated. Stiffening of the G-band mode and intensification of the defect-related D-band in the Raman spectra are also observed.

Diphenyl sulphoxide complexes of some divalent metal ions*1

Diphenyl sulphoxide (DPSO) complexes of some divalent metal perchlorates and chlorides are prepared The perchlorates of Mn, Co, Ni, Zn and Cd have the general formula [M(DPSO)6](CIO4)2. The Cu(II) complex is found to have the composition [Cu(DPSO)4] (CIO42. The chloro complex having the formula ZnCl2. 2DPSO, CdCl2.DPSO, HgCl2. DPSO and PdCl2. 2 DPSO have also been obtained. Infrared spectra indicate that the DPSO complexes of Mn, Co, Ni, Cu and Zn are oxygen-bonded while those of Cd, Hg and Pd are sulphur-bonded. The magnetic susceptibility and the optical spectral data reveal octahedral coordination for Mn, Co and Ni complexes. From the electronic spectra of Co and NI complexes, the ligand field parameters, Dq and β, are calculated.

Some sulphoxide complexes of iron

Diphenyl sulphoxide(DPSO) and dimethyl sulphoxide(DMSO) complexes of iron(II) having the composition [Fe(DPSO)6](ClO4)2, Fe(DPSO)2Cl2, Fe(DPSO)3Br2, Fe(DPSO)4I2, [Fe (DMSO)3Cl2]. DMSO and [Fe(DMSO)3Br2]. DMSO and DPSO complexes of iron(III), Fe(DPSO)2 Cl3 have been prepared and their physico-chemical properties studied. Their magnetic moments at room temperature show them to be spin-free complexes. The i.r. spectra reveal that oxygen is the donor atom in all the complexes. The electronic spectra of iron(II) complexes indicate octahedral coordination for the metal ion. A salt like structure [Fe(DPSO)4Cl2][FeCl4], is suggested for the iron (III) complex, where the cationic species has distorted octahedral structure while the anionic species has tetrahedral structure.

Cu(II) complexes of 1-benzyl-2-phenyl-benzimidazole

Copper(II) complexes of 1-benzyl-2-phenylbenzimidazole (BPBI) of the general formula Cu(BPBI)2X2, nH2O [X= Cl-, Br-, NO3 or OAc- (n = O) and X = NO3- or 1 2SO42-(n = 2H2O)] have been prepared. The complexes are found to be nonelectrolytes in nitrobenzene. Conductivity in nonaqueous media, magnetic susceptibilities and i.r. and electronic spectra of the complexes are reported. A tetragonally distorted octahedral structure has been suggested for these complexes.

Growth, self-assembly and dynamics of nano-scale films at fluid interfaces

Ultrathin films at fluid interfaces are important not only from a fundamental point of view as 2D complex fluids but have also become increasingly relevant in the development of novel functional materials. There has been an explosion in the synthesis work in this area over the last decade, giving rise to many exotic nanostructures at fluid interfaces. However, the factors controlling particle nucleation, growth and self-assembly at interfaces are poorly understood on a quantitative level. We will outline some of the recent attempts in this direction. Some of the selected investigations examining the macroscopic mechanical properties of molecular and particulate films at fluid interfaces will be reviewed. We conclude with a discussion of the electronic properties of these films that have potential technological and biological applications.

X-ray photoelectron spectroscopy of superconducting RuSr2Eu1.5Ce0.5Cu2O10 and nonsuperconducting RuSr2EuCeCu2O10

We report x-ray photoelectron spectroscopic investigation of RuSr2Eu1.5Ce0.5Cu2O10 with ferromagnetic T-C similar to 100 K and a superconducting transition temperature of similar to 30 K compared with RuSr2EuCeCu2O10, which is a ferromagnetic (T-C similar to 150 K) insulator. Our results show that the rare earths, Eu and Ce, are in 3+ and 4+ states, respectively. Comparing the Ru core level spectra from these compounds to those from two Ru reference oxides, we also show that Ru in these ruthenocuprates is always in 5+ state, suggesting that the doped holes in the superconducting compound arising from the substitution of Ce4+ by Eu3+ are primarily in the Cu-O plane, in close analogy to all other doped high-T-C cuprates. Analysis of Cu 2p spectra in terms of a configuration interaction model provides a quantitative description of the gross electronic structures of these ruthenocuprates.

Angle-resolved photoemission spectroscopy of the insulating NaxWO3: Anderson localization, polaron formation, and remnant Fermi surface

The electronic structure of the insulating sodium tungsten bronze, Na0.025WO3, is investigated by high-resolution angle-resolved photoemission spectroscopy. We find that near-E-F states are localized due to the strong disorder arising from random distribution of Na+ ions in the WO3 lattice, which makes the system insulating. The temperature dependence of photoemission spectra provides direct evidence for polaron formation. The remnant Fermi surface of the insulator is found to be the replica of the real Fermi surface in the metallic system

Quantitative structural refinement of mn K edge XANES in LaMnO3 and CaMnO3 perovskites

The special magnetotransport properties of hole doped manganese perovskites originate from a complex interplay among structural, magnetic and electronic degree of freedom. In this picture the local atomic structure around Mn ions plays a special role and this is the reason why short range order techniques like X-ray absorption spectroscopy (XAS) have been deeply exploited for studying these compounds. The analysis of near edge region features (XANES) of XAS spectra can provide very fine details of the local structure around Mn, complementary to the EXAFS, so contributing to the full understanding of the peculiar physical properties of these materials. Nevertheless the XANES analysis is complicated by the large amount of structural and electronic details involved making difficult the quantitative interpretation.This work exploits the recently developed MXAN code to achieve a full structural refinement of the Mn K edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3, in which the Mn ions are present only in one charge state as Mn3+ and Mn4+ respectively. The good agreement between the results derived from the analysis of near edge and extended region of the XAS spectra demonstrates that a quantitative picture of the local structure call be obtained from structural refinement of Mn K edge XANES data in these crystalline compounds. The XANES analysis offers, in addition.. the possibility to directly achieve information on the topology of local atomic structure around the absorber not directly achievable from EXAFS.

First-principles analysis of electron correlation, spin ordering and phonons in the normal state of FeSe1-x

We present first-principles density-functional-theory-based calculations to determine the effects of the strength of on-site electron correlation, magnetic ordering, pressure and Se vacancies on phonon frequencies and electronic structure of FeSe1-x. The theoretical equilibrium structure (lattice parameters) of FeSe depends sensitively on the value of the Hubbard parameter U of on-site correlation and magnetic ordering. Our results suggest that there is a competition between different antiferromagnetic states due to comparable magnetic exchange couplings between first- and second-neighbor Fe sites. As a result, a short range order of stripe antiferromagnetic type is shown to be relevant to the normal state of FeSe at low temperature. We show that there is a strong spin-phonon coupling in FeSe (comparable to its superconducting transition temperature) as reflected in large changes in the frequencies of certain phonons with different magnetic ordering, which is used to explain the observed hardening of a Raman-active phonon at temperatures (similar to 100 K) where magnetic ordering sets in. The symmetry of the stripe antiferromagnetic phase permits an induced stress with orthorhombic symmetry, leading to orthorhombic strain as a secondary order parameter at the temperature of magnetic ordering. The presence of Se vacancies in FeSe gives rise to a large peak in the density of states near the Fermi energy, which could enhance the superconducting transition temperature within the BCS-like picture.

Synthesis and characterization of Ti5Te4-type molybdenum cluster compounds, AxMo5As4(A = Cu, Al, or Ga)

A new series of molybdenum cluster compounds of the general formula AxMo5As4(A = Cu, Al, or Ga) has been synthesized. They are isostructural with the host Mo5As4(Ti5Te4-type) consisting of trans-vertex shared Mo6 octahedral chains. Investigations by X-ray photoelectron and Auger electron spectroscopies revealed a charge transfer from A to Mo5As4 in AxMo5As4. The occurrence of metallic (CuxMo5As4) and non-metallic (Al2Mo5As4 and Ga2Mo5As4) properties in this isostructural series of solids is consistent with the electronic structure of Ti5Te4-type solids involving M–M bonding in the cluster chains.