Electronic Structure of and the Metal-Insulator Transition in La1-xSrxCoO3-δ: A Soft-X-Ray Absorption Study

We report the soft-X-ray absorption spectra at the oxygen K-edge of La1-xSrxCoO3-δ (x = 0.0, 0.1, 0.2, 0.3 and 0.4) series with experimentally determined δ values. We show that the doping of holes by replacing La3+ with Sr2+ induces states within the band gap of the insulating undoped compound for small x and these doped states have a very substantial oxygen 2p character. This indicates that the insulating compounds belong to the charge transfer insulator regime. With increasing Sr content, the doped states broaden into a band overlapping the top of the primarily oxygen p-derived band, leading to an insulator-metal transition at x ≥ 0.2.

Electronic absorption and emission spectroscopic investigations of the interaction of the fullerenes, C60 and C70, with amines and aromatic molecules

Electronic absorption spectroscopy and fluorescence spectroscopy have been used to investigate the interaction of the fullerenes C60 and C70 with diethylaniline, and with aromatic solvents such as benzene. C60 interacts weakly with aromatic amines in the ground state while C70 does not interact at all. Steady state fluorescence emission and lifetime measurements show that both C60 and C70 form excited state complexes (exciplexes) with the amines in non-aromatic solvents such as methylcyclohexane, but not in benzene. In benzene, only fluorescence quenching is observed due to the interaction between the π systems of the aromatic solvent and the fullerene in the ground state. This is also borne out by the systematic study of solvent effects on the absorption and emission spectra of the fullerenes.

Electronic excitations and alternation of conjugated polymers

The electronic excitations and fluorescence of conjugated polymers are related to large or small alternation ? of the transfer integrals t(1 ± ?) along the backbone. The fluorescence of polysilanes (PSs) and poly (para-phenylenevinylene (PPV) is linked to large ?, which places the one-photon gap Eg below the lowest two-photon gap Ea and reduces distortions due to electron-phonon (e-p) coupling. In contrast to small ? not, vert, similar 0.1 in ?-conjugated polymers, such as polyacetylene (PA), para-conjugated phenyls lead to an extended ?-system with increased alternation, to states localized on each ring and to charge-transfer excitations between them. Surprisingly good agreement is found between semiempirical parametric method 3 (PM3) bond lengths and exact Pariser-Parr-Pople (PPP) ?-bond orders for trans-stilbene, where the PPV bipolarons are confined to two phenyls. Stilbene spectra are consistent with increased alternation and small e-p distortions.

Electronic structure of La1-xSrxFeO3

We have investigated the electronic structure of well-characterized samples of La1-xSrxFeO3 (x=0.0�0.4) by x-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy, bremsstrahlung isochromat (BI) spectroscopy, and Auger electron spectroscopy. We find systematic behavior in the occupied and unoccupied density of states reflecting changes in the electronic structure on hole doping via Sr substitution as well as providing estimates for different interaction strengths. The spectral features, particularly of the unoccupied states obtained from BI spectra, indicate the probable reason for the absence of an insulator-metal transition in this series. Analysis of the Auger spectra provides the estimates of the on-site effective Coulomb interaction strengths in Fe 3d and O 2p states. The parameter values for the bare charge-transfer energy ? and the Fe 3d�O 2p hybridization strength t? for LaFeO3 are obtained from an analysis of the Fe 2p core-level XPS in terms of a model many-body calculation. We discuss the character of the ground state in LaFeO3 as well as the nature of the doped hole states in La1-xSrxFeO3, based on these parameter values.

NDDO-based CI methods for the prediction of electronic spectra and sum-over-states molecular hyperpolarization

NDDO-based (AM1) configuration interaction (CI) calculations have been used to calculate the wavelength and oscillator strengths of electronic absorptions in organic molecules and the results used in a sum-over-states treatment to calculate second-order-hyperpolarizabilities. The results for both spectra and hyperpolarizabilities are of acceptable quality as long as a suitable CI-expansion is used. We have found that using an active space of eight electrons in eight orbitals and including all single and pair-double excitations in the CI leads to results that agree well with experiment and that do not change significantly with increasing active space for most organic molecules. Calculated second-order hyperpolarizabilities using this type of CI within a sum-over-states calculation appear to be of useful accuracy.

The Role of Electronic Word of Mouth in Shaping Consumer Attitudes

The purpose of this research was to investigate the role of electronic word of mouth (eWOM) in shaping consumer attitudes towards various products and services with concentration on the consumer attitude change. eWOM has long been proven to play an important role in influencing consumer attitudes and has been researched from a variety of perspectives. This study attempts to look deeper into the process of consumer attitude change by applying as the central theory of the study the Elaboration Likelihood Model of Persuasion by Petty and Cacioppo. In the processes of examining the background academic and empirical research the Internet and Web 2.0 are closely depicted in order to understand how throughout the past centuries technology allowed the rise of various mediums where consumers can not only share their opinions online about products and services but also communicate with other consumers. Manuel Castel’s Internet Galaxy, Gildin’s, Carl and Noland’s, Hennig-Thurau, Gwinner, Walsh and Gremler’s researches on eWOM are the central works that helped to shape both the theoretical and empirical parts of this study. The mixed method approach was chosen as a research method for this study. An online survey was conducted via the Surveymonkey.com platform and eight qualitative in-depth interviews were conducted. The results of the study show that central route queues as text quality and text argumentativeness are more prominent among the research subjects and the peripheral route queues: source credibility and source expertise did not show considerable significance. Also more experience and participation consumers have with user-rating websites and applications more inclined they are to elaborate on the central route cues and are more likely to search for opinions that they consider rational and credible. Also these respondents are less inclined to search for ratings that confirm their existing beliefs about products or services. Less experience/participation they have about eWOM more likely they are to search for reviews confirmatory to their own.

Do wordnets also improve human performance on NLP tasks?

FinnWordNet is a wordnet for Finnish that complies with the format of the Princeton WordNet (PWN) (Fellbaum, 1998). It was built by translating the PrincetonWordNet 3.0 synsets into Finnish by human translators. It is open source and contains 117000 synsets. The Finnish translations were inserted into the PWN structure resulting in a bilingual lexical database. In natural language processing (NLP), wordnets have been used for infusing computers with semantic knowledge assuming that humans already have a sufficient amount of this knowledge. In this paper we present a case study of using wordnets as an electronic dictionary. We tested whether native Finnish speakers benefit from using a wordnet while completing English sentence completion tasks. We found that using either an English wordnet or a bilingual English Finnish wordnet significantly improves performance in the task. This should be taken into account when setting standards and comparing human and computer performance on these tasks.

Tuning the electronic effective mass in double-doped SrTiO3

We elucidate the relationship between effective mass and carrier concentration in an oxide semiconductor controlled by a double-doping mechanism. In this model oxide system, Sr1-xLaxTiO3-delta, we can tune the effective mass ranging from 6 to 20m(e) as a function of filling (carrier concentration) and the scattering mechanism, which are dependent on the chosen lanthanum-and oxygen-vacancy concentrations. The effective mass values were calculated from the Boltzmann transport equation using the measured transport properties of thin films of Sr1-xLaxTiO3-delta. We show that the effective mass decreases with carrier concentration in this large-band-gap, low-mobility oxide, and this behavior is contrary to the traditional high-mobility, small-effective-mass semiconductors.

Correlated electronic states of C-60 fragments

We have studied electronic states of various fragments of C-60 within the Pariser-Parr-Pople (PPP) model and have obtained structural, magnetic and spectral properties of these molecules. The fragments studied include corannulene, fluoranthene and pyracylene. Pyracylene is studied using the exact valence bond (VB) approach while fluoranthene and corannulene are studied using a novel restricted CI technique which employs molecular orbitals for constructing the VB functions. The electronic excitations, bond order and ring currents are calculated for these systems. From these studies, the wide range of absorptions in C-60 can be viewed as those localized on pyracylene units or on the corannulene/fluoranthene units. The bond orders and ring currents show the hexagons to be similar to benzene rings. The pentagon-hexagon bonds are also found to be longer than the hexagon-hexagon bonds.

Electronic structure of early 3d-transition-metal oxides by analysis of the 2p core-level photoemission spectra

The electronic structures of a wide range of early transition-metal (TM) compounds, including Ti and V oxides with metal valences ranging from 2+ to 5+ and formal d-electron numbers ranging from 0 to 2, have been investigated by a configuration-interaction cluster model analysis of the core-level metal 2p x-ray photoemission spectra (XPS). Inelastic energy-loss backgrounds calculated from experimentally measured electron-energy-loss spectra (EELS) were subtracted from the XPS spectra to remove extrinsic loss features. Parameter values deduced for the charge-transfer energy Delta and the d-d Coulomb repulsion energy U are shown to continue the systematic trends established previously for the late TM compounds, giving support to a charge-transfer mechanism for the satellite structures. The early TM compounds are characterized by a large metal d-ligand p hybridization energy, resulting in strong covalency in these compounds. Values for Delta and U suggest that many early TM compounds should be reclassified as intermediate between the charge-transfer regime and the Mott-Hubbard regime.

meso-substituted octabromoporphyrins: Synthesis, spectroscopy, electrochemistry and electronic structure

The free-base, copper(II) and zinc(II) derivatives of 5,10,15,20-tetraarylporphyrin (aryl = phenyl, 4-methylphenyl or 4-chlorophenyl) and the corresponding brominated 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraarylporphyrin derivatives have been synthesized and their spectral and redox properties compared by UV/VIS, H-1 NMR, ESR and cyclic voltammetric methods. Substitution with the electron-withdrawing bromine groups at the pyrrole carbons has a profound influence on the UV/VIS and H-1 NMR spectral features and also on the redox potentials of these systems. On the other hand, electron-withdrawing chloro or electron-donating methyl groups at the para positions of the four phenyl rings have only a marginal effect on the spectra and redox potentials of both the brominated and the non-brominated derivatives. The ESR data for the copper(II) derivatives of ail these systems reveal that substitution at either the beta-pyrrole carbons and/or the para positions of the meso-phenyl groups does not significantly affect the spin-Hamiltonian parameters that describe the metal centre in each case. Collectively, these observations suggest that the highest-occupied (HOMO) and lowest-unoccupied molecular orbitals (LUMO) of the octabromoporphyrins involve the porphyrin pi-ring system as is the case with the non-brominated derivatives.-Investigations have been carried out to probe the electronic structures of these systems by three different approaches involving spectral and redox potential data as well as AMI calculations. The results obtained suggest that the electron-withdrawing beta-bromine substituents stabilize the LUMOs and, to a lesser degree, the HOMOs and that the extent of these changes can be fine-tuned, in a subtle way, by substituting at the meso-aryl rings of a given porphyrin.

Electronic conduction in LaNiO3-delta: the dependence on the oxygen stoichiometry delta

We report a systematic study of the electronic transport properties of the metallic perovskite oxide LaNiO3-delta as a function of the oxygen stoichiometry delta (delta less than or equal to 0.14). The electrical resistivity, magnetoresistance, susceptibility, Hall effect and thermopower have been studied, All of the transport coefficients are dependent on the value of delta. The resistivity increases almost exponentially as delta increases. We relate this increase in rho to the creation of Ni2+ with square-planar coordination. We find that there is a distinct T-1.5-contribution to the resistivity over the whole temperature range. The thermopower is negative, as expected for systems with electrons as the carrier, but the Hall coefficient is positive. We have given a qualitative and quantitative explanation for the different quantities observed and their systematic variation with the stoichiometry delta.

New La2CuO4 derivatives La(2-2x)Sr(2x)Cu(1-x)M(x)O(4) (M=Ti, Mn, Fe, or Ru): A study of linear Cu-O-M electronic interaction in two dimensions

Oxides of the general formula La2-2xSr2xCu1-xII,M(x)(IV)O(4) (M = Ti, Mn, Fe, or Ru), crystallizing in the tetragonal K,NIF, structure, have been synthesized. For M=Ti, only the x=0,5 member could be prepared, while for M=Mn and Fe, the composition range is 0 Cu(III)-O-Fe(III) valence degeneracy. Increasing the strontium content at the expense of lanthanum in La2-2xSr2xCu1-xFexO4 for x less than or equal to 0.20 renders the samples metallic but not superconducting. (C) 1997 Academic Press.

Structural evolution and electronic properties of La1+xSr2-xMn2O7

A detailed study of the layered manganite La1+xSr2-xMn2O7 has been performed, establishing that within the composition range 0.1 less than or equal to x less than or equal to 0.45 the phases crystallize in the I4/mmm space group. The evolution of structural parameters with x: in this composition range has been followed using a novel application of an existing program for the Rietveld analysis of powder diffraction data. The structure, a familiar intergrowth of rock-salt (La,Sr)O slabs and double perovskite (La,Sr)(2)Mn2O6 units, is characterized by a reluctance to deform the latter. This manifests as a ''pumping'' of the larger Sr-II ion into the 12-coordinate site of the structure as x is increased. We report these features of the structure as well as electrical transport and magnetic properties, in light of recent observations of giant, negative magnetoresistance in these systems.