Local-field and excitonic effects in the optical response of alpha-alumina

This paper introduces key ingredients of the dielectric response of a-alumina that go beyond an independent-particle (IP) treatment of the valence-electron excitations. The optical-response functions were calculated from first-principles both at the Bethe-Salpeter and the random-phase approximation (RPA) levels. Excitonic effects obtained within the Bethe-Salpeter framework were found essential for reproducing the low-energy part of the experimental spectra (below 15 eV) and the bound exciton in particular. For higher energies, local-field effects introduced through the RPA modified considerably the IP results and provided a satisfactory account of the reflectivity spectra and of the position and shape of the dominant bulk plasmon resonance in the electron energy-loss spectra.

Quasiparticle calculations of the electronic properties of ZrO2 and HfO2 polymorphs and their interface with Si

Quasiparticle calculations are performed to investigate the electronic band structures of various polymorphs of Hf and Zr oxides. The corrections with respect to density-functional-theory results are found to depend only weakly on the crystal structure. Based on these bulk calculations as well as those for bulk Si, the effect of quasiparticle corrections is also investigated for the band offsets at the interface between these oxides and Si assuming that the lineup of the potential at the interface is reproduced correctly within density-functional theory. On the one hand, the valence-band offsets are practically unchanged with a correction of a few tenths of electron volts. On the other hand, conduction-band offsets are raised by 1.3-1.5 eV. When applied to existing calculations for the offsets at the density-functional-theory level, our quasiparticle corrections provide results in good agreement with the experiment.

Electronic properties of zircon and hafnon from many-body perturbation theory

The electronic properties of zircon and hafnon, two wide-gap high-kappa materials, are investigated using many-body perturbation theory (MBPT) combined with the Wannier interpolation technique. For both materials, the calculated band structures differ from those obtained within density-functional theory and MBPT by (i) a slight displacement of the highest valence-band maximum from the Gamma point and (ii) an opening of the indirect band gap to 7.6 and 8.0 eV for zircon and hafnon, respectively. The introduction of vertex corrections in the many-body self-energy does not modify the results except for a global rigid shift of the many-body corrections.

Improved description of chemical barriers with generalized gradient approximations (GGAs) and meta-GGAs

The performance of exchange and correlation (xc) functionals of the generalized gradient approximation (GGA) type and of the meta-GGA type in the calculation of chemical reactions is related to topological features of the electron density which, in turn, are connected to the orbital structure of chemical bonds within the Kohn-Sham (KS) theory. Seventeen GGA and meta-GGA xc functionals are assessed for 15 hydrogen abstraction reactions and 3 symmetrical S(N)2 reactions. Systems that are problematic for standard GGAs characteristically have enhanced values of the dimensionless gradient argument s(sigma)(2) with local maxima in the bonding region. The origin of this topological feature is the occupation of valence KS orbitals with an antibonding or essentially nonbonding character. The local enhancement of s(sigma)(2) yields too negative exchange-correlation energies with standard GGAs for the transition state of the S(N)2 reaction, which leads to the reduced calculated reaction barriers. The unwarranted localization of the effective xc hole of the standard GGAs, i.e., the nondynamical correlation that is built into them but is spurious in this case, wields its effect by their s(sigma)(2) dependence. Barriers are improved for xc functionals with the exchange functional OPTX as x component, which has a modified dependence on s(sigma)(2). Standard GGAs also underestimate the barriers for the hydrogen abstraction reactions. In this case the barriers are improved by correlation functionals, such as the Laplacian-dependent (LAP3) functional, which has a modified dependence on the Coulomb correlation of the opposite- and like-spin electrons. The best overall performance is established for the combination OLAP3 of OPTX and LAP3.

On the required shape corrections to the local density and generalized gradient approximations to the Kohn-Sham potentials for molecular response calculations of (hyper)polarizabilities and excitation energies

It is well known that shape corrections have to be applied to the local-density (LDA) and generalized gradient (GGA) approximations to the Kohn-Sham exchange-correlation potential in order to obtain reliable response properties in time dependent density functional theory calculations. Here we demonstrate that it is an oversimplified view that these shape corrections concern primarily the asymptotic part of the potential, and that they affect only Rydberg type transitions. The performance is assessed of two shape-corrected Kohn-Sham potentials, the gradient-regulated asymptotic connection procedure applied to the Becke-Perdew potential (BP-GRAC) and the statistical averaging of (model) orbital potentials (SAOP), versus LDA and GGA potentials, in molecular response calculations of the static average polarizability alpha, the Cauchy coefficient S-4, and the static average hyperpolarizability beta. The nature of the distortions of the LDA/GGA potentials is highlighted and it is shown that they introduce many spurious excited states at too low energy which may mix with valence excited states, resulting in wrong excited state compositions. They also lead to wrong oscillator strengths and thus to a wrong spectral structure of properties like the polarizability. LDA, Becke-Lee-Yang-Parr (BLYP), and Becke-Perdew (BP) characteristically underestimate contributions to alpha and S-4 from bound Rydberg-type states and overestimate those from the continuum. Cancellation of the errors in these contributions occasionally produces fortuitously good results. The distortions of the LDA, BLYP, and BP spectra are related to the deficiencies of the LDA/GGA potentials in both the bulk and outer molecular regions. In contrast, both SAOP and BP-GRAC potentials produce high quality polarizabilities for 21 molecules and also reliable Cauchy moments and hyperpolarizabilities for the selected molecules. The analysis for the N-2 molecule shows, that both SAOP and BP-GRAC yield reliable energies omega(i) and oscillator strengths f(i) of individual excitations, so that they reproduce well the spectral structure of alpha and S-4.(C) 2002 American Institute of Physics.

The failure of generalized gradient approximations (GGAs) and meta-GGAs for the two-center three-electron bonds in He-2(+), (H2O)(2)(+), and (NH3)(2)(+)

The radical cations He-2(+) (H2O)(2)(+), and (NH3)(2)(+) with two-center three-electron A-A bonds are investigated at the configuration interaction (CI), accurate Kohn-Sham (KS), generalized gradient approximation (GGA), and meta-GGA levels. Assessment of seven different GGA and six meta-GGA methods shows that the A(2)(+) systems remain a difficult case for density functional theory (DFT). All methods tested consistently overestimate the stability of A(2)(+): the corresponding D-e errors decrease for more diffuse valence densities in the series He-2(+) > (H2O)(2)(+) > (NH3)(2)(+). Upon comparison to the energy terms of the accurate Kohn-Sham solutions, the approximate exchange functionals are found to be responsible for the errors of GGA-type methods, which characteristically overestimate the exchange in A(2)(+). These so-called exchange functionals implicitly use localized holes. Such localized holes do occur if there is left-right correlation, i.e., the exchange functionals then also describe nondynamical correlation. However, in the hemibonded A(2)(+) systems the typical molecular (left-right, nondynamical) correlation of the two-electron pair bond is absent. The nondynamical correlation built into the exchange functionals is then spurious and yields too low energies.

Magnetic and electronic structure of TICo2S2

An extensive investigation of the ferromagnetic compound TlCo2S2 has resulted in new information on the electronic and magnetic structure. Electronic structure calculations showed that magnetic ordering is energetically favorable with a clear driving force for ferromagnetic coupling within the cobalt layers. TlCo2S2 is metallic and the conductivity is due to holes in the valence band. XPS single crystal measurements did not show evidence of mixed oxidation states of cobalt. Neutron powder diffraction resulted in a ferromagnetic structure with the magnetic moment in the ab-plane. The derived magnetic moment of the cobalt atom is 0.65(2) mu(B) at 10 K and is in very good agreement with the value, mu(sat) = 0.65(1) mu(B) at 10 K, inferred from the magnetic hysteresis curve. (C) 2004 Elsevier Inc. All rights reserved.

Unusual photoresponse of indium doped ZnO/organic thin film heterojunction

Photoresponse of n-type indium-doped ZnO and a p-type polymer (PEDOT:PSS) heterojunction devices are studied, juxtaposed with the photoluminescence of the In-ZnO samples. In addition to the expected photoresponse in the ultraviolet, the heterojunctions exhibit significant photoresponse to the visible (532 nm). However, neither the doped ZnO nor PEDOT: PSS individually show any photoresponse to visible light. The sub-bandgap photoresponse of the heterojunction originates from visible photon mediated e-h generation between the In-ZnO valence band and localized states lying within the band gap. Though increased doping of In-ZnO has limited effect on the photoluminescence, it significantly diminishes the photoresponse. The study indicates that optimally doped devices are promising for the detection of wavelengths in selected windows in the visible. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4704655]

Structural and electronic properties of Ce overlayers and low-dimensional Pt-Ce alloys on Pt{111}

The structural, thermal, chemisorptive, and electronic properties of Ce on Pt{111} are studied by photoemission, Auger spectroscopy, scanning tunnel microscope (STM), and low-energy electron diffraction (LEED). Stranski-Krastanov-like growth of low-density Ce layers is accompanied by substantial valence charge transfer from Ce to Pt: in line with this, the measured dipole moment and polarizability of adsorbed Ce at low coverages are 7.2 x 10(-30) C m and similar to 1.3x10(-29) m(3), respectively. Pt-Ce intermixing commences at similar to 400 K and with increasing temperature a sequence of five different ordered surface alloys evolves. The symmetry, periodicities, and rotational epitaxy observed by LEED are in good accord with the STM data which reveal the true complexity of the system. The Various bimetallic surface phases are based on growth of crystalline Pt5Ce, a hexagonal layer structure consisting of alternating layers of Pt2Ce and Kagome nets of Pt atoms. This characteristic ABAB layered arrangement of the surface alloys is clearly imaged, and chemisorption data permit a distinction to be made between the more reactive Pt2Ce layer and the less reactive Pt Kagome net. Either type of layer can appear at the surface as the terminating structure, thicker films exhibiting unit mesh parameters characteristic of the bulk alloy.

Chemoenzymatic synthesis of monocyclic arene oxides and arene hydrates from substituted benzene substrates

Enantiopure cis-dihydrodiol bacterial metabolites of substituted benzene substrates were used as precursors, in a chemoenzymatic synthesis of the corresponding benzene oxides and of a substituted oxepine, via dihydrobenzene oxide intermediates. A rapid total racemization of the substituted benzene 2,3-oxides was found to have occurred, via their oxepine valence tautomers, in accord with predictions and theoretical calculations. Reduction of a substituted arene oxide to yield a racemic arene hydrate was observed. Arene hydrates have also been synthesised, in enantiopure form, from the corresponding dihydroarene oxide or trans-bromoacetate precursors. Biotransformation of one arene hydrate enantiomer resulted in a toluene-dioxygenase catalysed cis-dihydroxylation to yield a benzene cis-triol metabolite.

Organic synthesis in the interstellar medium by low-energy carbon irradiation

We present a first principles molecular dynamics (FPMD) study of the interaction of low-energy neutral carbon projectiles with amorphous solid water clusters at 30 K. Reactions involving the carbon atom at an initial energy of 11 and 1.7 eV with 30-molecule clusters have been investigated. Simulations indicate that the formation of hydroxymethylene, an intermediate in formaldehyde production, dominates at the higher energy. The reaction proceeds by fragmenting a water molecule, binding the carbon to the OH radical, and saturating the C valence with a hydrogen atom that can arise from the originally dissociated water molecule, or through a chain of proton transfer events. We identified several possible pathways for the formation of HCOH. When the initial collision occurs at the periphery of the cluster, we observe the formation of CO and the evaporation of water molecules. At the lower energy water fragmentation is not favorable, thus leading to the formation of weakly bound carbon-water complexes. © 2013 American Chemical Society.

Oxytocin effects on neural correlates of self-referential processing

Oxytocin (OT) influences how humans process information about others. Whether OT affects the processing of information about oneself remains unknown. Using a double-blind, placebo-controlled within-subject design, we recorded event-related potentials (ERPs) from adults during trait judgments about oneself and a celebrity and during judgments on word valence, after intranasal OT or placebo administration. We found that OT vs. placebo treatment reduced the differential amplitudes of a fronto-central positivity at 220-280 ms (P2) during self- vs. valence-judgments. OT vs. placebo treatment tended to reduce the differential amplitude of a late positive potential at 520-1000 ms (LPP) during self-judgments but to increase the differential LPP amplitude during other-judgments. OT effects on the differential P2 and LPP amplitudes to self- vs. celebrity-judgments were positively correlated with a measure of interdependence of self-construals. Thus OT modulates the neural correlates of self-referential processing and this effect varies as a function of interdependence.

Using Brain Data for Sentiment Analysis

We present the results of exploratory experiments using lexical valence extracted from brain using electroencephalography (EEG) for sentiment analysis. We selected 78 English words (36 for training and 42 for testing), presented as stimuli to 3 English native speakers. EEG signals were recorded from the subjects while they performed a mental imaging task for each word stimulus. Wavelet decomposition was employed to extract EEG features from the time-frequency domain. The extracted features were used as inputs to a sparse multinomial logistic regression (SMLR) classifier for valence classification, after univariate ANOVA feature selection. After mapping EEG signals to sentiment valences, we exploited the lexical polarity extracted from brain data for the prediction of the valence of 12 sentences taken from the SemEval-2007 shared task, and compared it against existing lexical resources.

A comparison of the effectiveness of TiO2 photocatalysis and UVA photolysis for the destruction of three pathogenic micro-organisms

TiO₂ photocatalysis has demonstrated efficacy as a treatment process for water contaminated with chemical pollutants. When exposed to UVA light TiO₂ also demonstrates an effective bactericidal activity. The mechanism of this process has been reported to involve attack by valence band generated hydroxyl radicals. In this study when three common bacterial pathogens, Escherichia coli, Salmonella enterica serovar Enteritidis and Pseudomonas aeruginosa, were exposed to TiO₂ and UVA light a substantial decrease in bacterial numbers was observed. Control experiments in which all three pathogens were exposed to UVA light only resulted in a similar reduction in bacterial numbers. Moreover, exposure to UVA light alone resulted in the production of a smaller than average colony phenotype among the surviving bacteria, for all three pathogens examined, a finding which was not observed following treatment with UVA and TiO₂. Small slow growing colonies have been described for several pathogenic bacteria and are referred to as small colony variants. Several studies have demonstrated an association between small colony variants and persistent, recurrent and antibiotic resistant infections. We propose that the production of small colony variants of pathogenic bacteria following UVA treatment of drinking water may represent a health hazard. As these small colony variants were not observed with the UVA/TiO₂ system this potential hazard is not a risk when using this technology. It would also appear that the bactericidal mechanism is different with the UVA/TiO₂ process compared to when UVA light is used alone.

Unidirectional suppression of hydrogen oxidation on oxidized platinum clusters

Solar-driven water splitting to produce hydrogen may be an ideal solution for global energy and environment issues. Among the various photocatalytic systems, platinum has been widely used to co-catalyse the reduction of protons in water for hydrogen evolution. However, the undesirable hydrogen oxidation reaction can also be readily catalysed by metallic platinum, which limits the solar energy conversion efficiency in artificial photosynthesis. Here we report that the unidirectional suppression of hydrogen oxidation in photocatalytic water splitting can be fulfilled by controlling the valence state of platinum; this platinum-based cocatalyst in a higher oxidation state can act as an efficient hydrogen evolution site while suppressing the undesirable hydrogen back-oxidation. The findings in this work may pave the way for developing other high-efficientcy platinum-based catalysts for photocatalysis, photoelectrochemistry, fuel cells and water-gas shift reactions.