Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn

Chemical state X-ray photoelectron spectroscopic analysis of first row transition metals and their oxides and hydroxides is challenging due to the complexity of the 2p spectra resulting from peak asymmetries, complex multiplet splitting, shake-up and plasmon loss structure, and uncertain, overlapping binding energies. A review of current literature shows that all values necessary for reproducible, quantitative chemical state analysis are usually not provided. This paper reports a more consistent, practical and effective approach to curve-fitting the various chemical states in a variety of Sc, Ti, V, Cu and Zn metals, oxides and hydroxides. The curve-fitting procedures proposed are based on a combination of (1) standard spectra from quality reference samples, (2) a survey of appropriate literature databases and/or a compilation of the literature references, and (3) specific literature references where fitting procedures are available. Binding energies, full-width at half maximum (FWHM) values, spin-orbit splitting values, asymmetric peak-shape fitting parameters, and, for Cu and Zn, Auger parameters values are presented. The quantification procedure for Cu species details the use of the shake-up satellites for Cu(II)-containing compounds and the exact binding energies of the Cu(0) and Cu(I) peaks. The use of the modified Auger parameter for Cu and Zn species allows for corroborating evidence when there is uncertainty in the binding energy assignment. These procedures can remove uncertainties in analysis of surface states in nano-particles, corrosion, catalysis and surface-engineered materials.     

Presynaptic action of neurotensin on dopamine release through inhibition of D2 receptor function

Background  

Neurotensin (NT) is known to act on dopamine (DA) neurons at the somatodendritic level to regulate cell firing and secondarily enhance DA release. In addition, anatomical and indirect physiological data suggest the presence of NT receptors at the terminal level. However, a clear demonstration of the mechanism of action of NT on dopaminergic axon terminals is lacking. We hypothesize that NT acts to increase DA release by inhibiting the function of terminal D2 autoreceptors. To test this hypothesis, we used fast-scan cyclic voltammetry (FCV) to monitor in real time the axonal release of DA in the nucleus accumbens (NAcc).     

More is the Same; Phase Transitions and Mean Field Theories

This paper is the first in a series that will look at the theory of phase transitions from the perspectives of physics and the philosophy of science. The series will consider a group of related concepts derived from condensed matter and statistical physics. The key technical ideas go under the names of “singularity”, “order parameter”, “mean field theory”, “variational method”, “correlation length”, “universality class”, “scale changes”, and “renormalization”. The first four of these will be considered here. In a less technical vein, the question here is how can matter, ordinary matter, support a diversity of forms. We see this diversity each time we observe ice in contact with liquid water or see water vapor (steam) come up from a pot of heated water. Different phases can be qualitatively different in that walking on ice is well within human capacity, but walking on liquid water is proverbially forbidden to ordinary humans. These differences have been apparent to humankind for millennia, but only brought within the domain of scientific understanding since the 1880s. A phase transition is a change from one behavior to another. A first order phase transition involves a discontinuous jump in some statistical variable. The discontinuous property is called the order parameter. Each phase transition has its own order parameter. The possible order parameters range over a tremendous variety of physical properties. These properties include the density of a liquid-gas transition, the magnetization in a ferromagnet, the size of a connected cluster in a percolation transition, and a condensate wave function in a superfluid or superconductor. A continuous transition occurs when the discontinuity in the jump approaches zero. This article is about statistical mechanics and the development of mean field theory as a basis for a partial understanding of phase transition phenomena. Much of the material in this review was first prepared for the Royal Netherlands Academy of Arts and Sciences in 2006. It has appeared in draft form on the authors’ web site (http://jfi.uchicago.edu/~leop/) since then. The title of this article is a hommage to Philip Anderson and his essay “More is Different” (Sci. New Ser. 177(4047):393–396, 1972; N.-P. Ong and R. Bhatt (eds.) More is Different: Fifty Years of Condensed Matter Physics, Princeton Series in Physics, Princeton University Press, 2001) which describes how new concepts, not applicable in ordinary classical or quantum mechanics, can arise from the consideration of aggregates of large numbers of particles. Since phase transitions only occur in systems with an infinite number of degrees of freedom, such transitions are a prime example of Anderson’s thesis.     

Azide reactions for controlling clean silicon surface chemistry: benzylazide on Si(100)-2 x 1

A combination of experimental and computational studies presents direct proof of a novel reaction pathway that delivers aromatic compounds onto a Si(100)-2 x 1 substrate. Benzylazide chemisorbs on a Si(100)-2 x 1 surface, and this chemisorption is followed by nitrogen elimination, leading to a stable surface adduct based on a Si-Si-N cyclic entity. This reaction occurs via a stable surface intermediate with the surface-bound nitrogen molecule stabilized by the presence of a neighboring aromatic group, which eventually releases nitrogen into the gas phase and forms the final product.     

Gold nanoelectrode ensembles for direct trace electroanalysis of iodide

A procedure for the standardization of ensembles of gold nanodisk electrodes (NEE) of 30 nm diameter is presented, which is based on the analytical comparison between experimental cyclic voltammograms (CV) obtained at the NEEs in diluted solutions of redox probes and CV patterns obtained by digital simulation. Possible origins of defects sometimes found in NEEs are discussed. Selected NEEs are then employed for the study of the electrochemical oxidation of iodide in acidic solutions. CV patterns display typical quasi-reversible behavior which involves associated chemical reactions between adsorbed and solution species. The main CV characteristics at the NEE compare with those observed at millimeter sized gold disk electrodes (Au-macro), apart a slight shift in E_1/2 values and slightly higher peak to peak separation at the NEE. The detection limit (DL) at NEEs is 0.3 μM, which is more than one order of magnitude lower than DL at the Au-macro (4 μM). The mechanism of the electrochemical oxidation of iodide at NEEs is discussed. Finally, NEEs are applied to the direct determination of iodide at micromolar concentration levels in real samples, namely in some ophthalmic drugs and iodized table salt.     

Optimization of microwave digestion for mercury determination in marine biological samples by cold vapour atomic absorption spectrometry

Optimization of acid digestion method for mercury determination in marine biological samples (dolphin liver, fish and mussel tissues) using a closed vessel microwave sample preparation is presented. Five digestion procedures with different acid mixtures were investigated: the best results were obtained when the microwave-assisted digestion was based on sample dissolution with HNO3-H2SO4-K2Cr2O7 mixture. A comparison between microwave digestion and conventional reflux digestion shows there are considerable losses of mercury in the open digestion system. The microwave digestion method has been tested satisfactorily using two certified reference materials. Analytical results show a good agreement with certified values. The microwave digestion proved to be a reliable and rapid method for decomposition of biological samples in mercury determination.     

Absolute and Convective Instabilities of Semi-bounded Spatially Developing Flows

We analyse the absolute and convective instabilities of, and spatially amplifying waves in, semi-bounded spatially developing flows and media by applying the Laplace transform in time to the corresponding initial-value linear stability problem and treating the resulting boundary-value problem on ?⁺ for a vector equation as a dynamical system. The analysis is an extension of our recently developed linear stability theory for spatially developing open flows and media with algebraically decaying tails and for fronts to flows in a semi-infinite domain. We derive the global normal-mode dispersion relations for different domains of frequency and treat absolute instability, convectively unstable wave packets and signalling. It is shown that when the limit state at infinity, i.e. the associated uniform state, is stable, the inhomogeneous flow is either stable or absolutely unstable. The inhomogeneous flow is absolutely stable but convectively unstable if and only if the flow is globally stable and the associated uniform state is convectively unstable. In such a case signalling in the inhomogeneous flow is identical with signalling in the associated uniform state.     

A study of (<Emphasis Type="Italic">x</Emphasis>(<Emphasis Type="Italic">q</Emphasis> + 1), <Emphasis Type="Italic">x</Emphasis>; 2, <Emphasis Type="Italic">q</Emphasis>)-minihypers

In this paper, we study the weighted (x(q + 1), x; 2, q)-minihypers. These are weighted sets of x(q + 1) points in PG(2, q) intersecting every line in at least x points. We investigate the decomposability of these minihypers, and define a switching construction which associates to an (x(q + 1), x; 2, q)-minihyper, with x ≤ q ² − q, not decomposable in the sum of another minihyper and a line, a (j(q + 1), j; 2, q)-minihyper, where j = q ² − q − x, again not decomposable into the sum of another minihyper and a line. We also characterize particular (x(q + 1), x; 2, q)-minihypers, and give new examples. Additionally, we show that (x(q + 1), x; 2, q)-minihypers can be described as rational sums of lines. In this way, this work continues the research on (x(q + 1), x; 2, q)-minihypers by Hill and Ward (Des Codes Cryptogr 44:169–196, 2007), giving further results on these minihypers.     

Kullback–Leibler quantum divergence as an indicator of quantum chaos

We discuss a system of a nonlinear Kerr-like oscillator externally pumped by ultra-short, coherent pulses. For such a system, we analyse the application of the Kullback–Leibler quantum divergence K[ρ||σ]$K[\rho ||\sigma ]$ to the detection of quantum chaotic behaviour. Defining linear and nonlinear quantum divergences, and calculating their power spectra, we show that these parameters are more suitable indicators of quantum chaos than the fidelity commonly discussed in the literature, and are useful for dealing with short time series. Moreover, the nonlinear divergence is more sensitive to chaotic bands and to boundaries of chaotic regions, compared to its linear counterpart.     

Beam-target double-spin asymmetry A{LT} in charged pion production from deep inelastic scattering on a transversely polarized {3}He target at 1.4<Q{2}<2.7 GeV{2}

We report the first measurement of the double-spin asymmetry A{LT} for charged pion electroproduction in semi-inclusive deep-inelastic electron scattering on a transversely polarized {3}He target. The kinematics focused on the valence quark region, 0.16相似文献