ELECTROCHEMICAL STUDY OF ISOPOLY AND HETEROPOLY OXOMETALLATE FILM MODIFIED MICROELECTRODES .5. PREPARATION AND ELECTROCHEMICAL-BEHAVIOR OF A 2/18-MOLYBDODIPHOSPHATE ANION MONOLAYER MODIFIED ELECTRODE

In this paper a carbon fibre (CF) microelectrode modified with the 2:18-molybdodiphosphate anion by simple adsorption is described and its electrochemical behaviour is reported. The 2:18-molybdodiphosphate anion (alpha-P2Mo18O626-), which is a Dawson structure, undergoes five successive multielectron reductions in acidic solution. The first three redox waves correspond to the two-electron process, and the last two waves are four-electron and six-electron processes respectively. On the basis of the experimental results it is shown that the electrode process of alpha-P2Mo18O626- on the CF electrode in acidic solution is simultaneously controlled by the diffusion and adsorption of alpha-P2Mo18O626- anions. When the concentration of the alpha-P2Mo18O626- in the solution is reduced, the electrode process mainly exhibits non-diffusion-controlled behaviour, and the diffusion-limited process takes over as the concentration of alpha-P2Mo18O626- becomes higher. The CF electrode modified with a thin film of alpha-P2Mo18O626- exhibits very good stability and redox behaviour in aqueous acidic solution. The alpha-P2Mo18O626- is reduced to heteropoly blue, with an accompanying protonation process. The addition of more than six electrons to the alpha-P2Mo18O626- anion in an aqueous solution does not result in its decomposition. The result obtained is not the same as that reported previously.

ANALYSIS OF ANGULAR OVERLAP PARAMETERS FOR EU3+ - LN2O2S (LN = LU, Y, GD, LA) CRYSTAL SERIES

The angular overlap model (AOM) is applied to 4f6 electron systems. The crystal field parameters are interpreted and covalency between 4f electrons and ligands is investigated based on the experimental energy levels. For Eu3+:Ln2O2S (Ln = Lu, Y, Gd, La) crystal series, we adopt two computational schemes. First of all, we assume that the distances to all ligands are equal, and then the distances to all ligands are divided into two groups, namely, oxygens as one group, sulfurs as the other. Of course, much information about covalency will be obtained from the latter case. Obviously, our results show that the covalency of Ln-O bonding is stronger than that of Ln-S bonding in line with much shorter bondlength for the former than that for the latter. The two schemes yield the same results, that is, for sigma and pi bonding, ligands are strong donors as well as sigma, pi effects are dominant over delta, phi effects.

ELECTROCHEMICAL STUDY OF ISOPOLY-OXOMETALLATE AND HETEROPOLY-OXOMETALLATE FILM MODIFIED MICROELECTRODES .2. ELECTROCHEMICAL-BEHAVIOR OF ISOPOLYMOLYBDIC ACID MONOLAYER MODIFIED CARBON-FIBER MICROELECTRODES

In this paper the electrochemical properties of isopolymolybdic anion thin film modified carbon fibre (CF) microelectrode prepared by simple dip coating have been described. The modified electrode shows three couples of surface redox waves between + 0.70 and - 0.1 V vs. sce in 2 M H2SO4 solution with good stability and reversibility. The pH of solution has a marked effect on the electrochemical behaviour and stability of the film, the stronger the acidity of electrolyte solution is, the better the stability and reversibility of isopolymolybdic anion film CF microelectrode will be. The scanning potential range strongly influences on the electrochemical behaviour of the film. The isopolymolybdic anion film prepared by the dip coating resulting a monolayer with estimated surface concentration (F) 2.8 x 10(-11) mol cm-2. From the half-peak widths and peak areas of the surface redox waves of the film electrode, the first three surface waves are corresponding to two-electron processes. The electron energy spectra show the products by six electrons reduction are a mixture of Mo(VI) and Mo(V) species. The electrochemical reaction of the isopolymolybdic anion monolayer can be expressed as Mo8O264- + mH+ + 2ne half arrow right over half arrow left [HmMo8-2n(VI)Mo2n(V)O26](4,2n-m)-n = 1, 2, 3; m = 2, 5, 7.

OBSERVATION OF MOSSBAUER-EFFECT IN THE HIGH-TEMPERATURE SUPERCONDUCTOR EUBA2CU3O7-X WITH DC ELECTRIC-CURRENT

The difference between the Mossbauer parameters for EuBa2Cu3O7-x with dc electric current and those without dc electric current at 83 K has been observed. The change in isomer shift, electric quadrupole splitting and the asymmetry parameter of the electric field gradient at the Eu-151 nucleus may be caused by the movement of a mass of conduction electrons along a certain direction in the EuBa2Cu3O7-x crystal with a layered structure.

低能髙流强电子束在绝缘管中的导向效应研究

带电粒子与绝缘体表面相互作用的研究揭示了很多新的物理现象和物理规律，目前该研究领域已拓展到原子物理，固体物理，等离子体物理等领域，特别是促进了纳米材料，超小尺寸半导体芯片制作，固体结构分析等应用领域的发展。本论文介绍了低能高流强电子束与绝缘体相互作用实验平台的建设，包括强流LaB6电子枪，64通道一维位置灵敏法拉第筒，电流电压转换放大器，基于Lab VIEW的数据获取软件系统等。研究了低能高流强电子束与锥形绝缘毛细管之间的相互作用。测量了出射电子的角分布与能谱，研究了入射电子能量、流强对电子传输效率的影响，分析了电子与高电荷态粒子同毛细管相互作用的区别。用低能高流强电子束与等内径弯曲绝缘管相互作用，测量了出射电子的角分布，研究了入射能量与流强对导向效应的影响。研究表明，与高点和态离子相比，电子与绝缘管相互作用有许多新的特性，电子传输效率较高电荷态粒子小1-2个数量级，且能量损失严重。量子反射和多次小角度散射是电子导向的主要原因

The structure of Aquifex aeolicus sulfide:quinone oxidoreductase, a basis to understand sulfide detoxification and respiration

Sulfide: quinone oxidoreductase (SQR) is a flavoprotein with homologues in all domains of life except plants. It plays a physiological role both in sulfide detoxification and in energy transduction. We isolated the protein from native membranes of the hyperthermophilic bacterium Aquifex aeolicus, and we determined its X-ray structure in the "as-purified,'' substrate-bound, and inhibitor-bound forms at resolutions of 2.3, 2.0, and 2.9 angstrom, respectively. The structure is composed of 2 Rossmann domains and 1 attachment domain, with an overall monomeric architecture typical of disulfide oxidoreductase flavoproteins. A. aeolicus SQR is a surprisingly trimeric, periplasmic integral monotopic membrane protein that inserts about 12 angstrom into the lipidic bilayer through an amphipathic helix-turn-helix tripodal motif. The quinone is located in a channel that extends from the si side of the FAD to the membrane. The quinone ring is sandwiched between the conserved amino acids Phe-385 and Ile-346, and it is possibly protonated upon reduction via Glu-318 and/or neighboring water molecules. Sulfide polymerization occurs on the re side of FAD, where the invariant Cys-156 and Cys-347 appear to be covalently bound to polysulfur fragments. The structure suggests that FAD is covalently linked to the polypeptide in an unusual way, via a disulfide bridge between the 8-methyl group and Cys-124. The applicability of this disulfide bridge for transferring electrons from sulfide to FAD, 2 mechanisms for sulfide polymerization and channeling of the substrate, S2-, and of the product, S-n, in and out of the active site are discussed.

Aminic nitrogen-bearing polydentate Schiff base compounds as corrosion inhibitors for iron in acidic media: A quantum chemical calculation

Quantum chemical calculations based on DFT method were performed on three polydentate Schiff base compounds (PSCs) used as corrosion inhibitors for iron in acid media to determine the relationship between the molecular structure of PSC and inhibition efficiency. The structural parameters, such as the frontier molecular orbital energy HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital), the charge distribution of the studied inhibitors, the absolute electronegativity (chi) values, and the fraction of electrons (Delta N) transfer from inhibitors to iron, were also calculated and correlated with inhibition efficiencies. The results showed that the inhibition efficiency of PSCs increased with the increase in E-HOMO and decrease in E-LUMO-E-HOMO; and the areas containing N atoms are most possible sites for bonding the metal iron surface by donating electrons to the metal. (C) 2007 Elsevier Ltd. All rights reserved.

压力和铁含量对铁方镁石(Mg1-xFex)O(x<=0.25)弹性常数影响的第一性原理研究

By first principle methods based on density functional theory (DFT),the equation of state(EOS) and elastic constants of both periclase and ferropericlase are calculated. The pressure and iron doping effects on the elastic constants of ferropericlase are investigated systematically. Firstly, we calculate the elastic constants of periclase and compare the obtained results with experimental data and other theoretical calculations, which shows a encouraging consistence and demonstrates the practicability of first-principle methods. Secondly, by adding iron into periclase crystal model, we build up ferropericlase with iron contents ranging from 0% to 25% mole percent. The corresponding elastic constants are calculated in a large pressure range(0~120GPa). Emphatically, the strong correlation of 3d electrons in transitional elements, such as iron, is difficult to treat in first-principle methods for a long time. The current solution is to make additional correction. During the initial stage of this study, the strong correlation of 3d electrons in iron is not considered, and we observed that addition of iron decreases the volume of ferropericlase, which is totally contradictory to the experimental data. By applying LDA+U approximation in order to solve the strongly correlated 3d electron of iron, we observed the expansion of volume by iron as expected. On the basis of the LDA+U approximation, the elastic constants of ferropericlase are calculated. After a detailed analysis of data obtained from theoretical calculations, we have reached the following conclusions:(1)pressure imposes positive effects on all elastic constants, and the degree of effects is C11>C12>C44. (2) Iron has no distinctive effects on C11 and C12, although some fluctuations are observed around 60GPa. However, iron has obvious softening effects on C44 The softening effects on C44 are intensified as pressure increases. Above the 100GPa, the effects increase greatly, even surpasses the pressure's positive effects in ferropericlase crystal models with iron mole percent of having 12.5%, 18.75% and 25% iron content. (3)As to the modulus deprived from elastic constants, iron has no effect on the adiabatic bulk module BS, only a little fluctuation around 60GPa. We find iron's softening effects on shear modulus G. (4)We find out that, compared with low iron content, elastic constants with iron content approaching 25mole% is consistently fluctuated，which may be caused by the limitations of the LDA+U approximation method itself. (5)We investigate the pressure and Fe doping effects on elastic anisotropy factor（A=(2C44+C12-C11)/C11） of ferropericlase and find out that iron contents will lower the critical isotropic pressure. At the same pressure, when the pressure is below the isotropic pressure, iron softens the anisotropy factor ; when pressure surpasses the isotropic pressure, iron increases the anisotropy factor.

Covariance analysis of the Coulomb explosion of ammonia induced by intense nanosecond laser at 532 nm

The Coulomb explosion of ammonia clusters induced by nanosecond laser at 532 not with an intensity of similar to 10(12) Wcm(-2) has been studied by time of flight mass spectrometry. The dominant multiply charged ions are N3+ and N2+ with kinetic energies of 110 and 50 eV respectively. The electrons generated from the multiphoton ionization are heated through inverse bremsstrahlung by the laser field when colliding with neutral or ionic particles. When their energies surpass the corresponding ionization potentials of the molecules or ions, the subsequent electron impact ionization may take place thus resulting in multi-charged nitrogen ions. Covariance analysis is made to study the possible pathways of the Coulomb explosion.

Cluster-assistant generation of multiply charged atomic ions in nanosecond laser ionization of seeded methyl iodide beam

The photoionization of methyl iodide beam seeded in argon and helium is studied by time-of-flight mass spectrometry using a 25 ns, 532 nm Nd-YAG laser with intensities in the range of 2 x 10(10)-2 x 10(11) W/cm(2). Multiply charged ions Of Iq+ (q = 2-3) and C2+ with tens of eV kinetic energies have been observed when laser interacts with the middle part of the pulsed molecular beam, whose peak profiles are independent on the laser polarization directions. Strong evidences show that these ions are coming from the Coulomb explosion of multiply charged CH3I clusters, and laser induced inverse bremsstrahlung absorption of caged electrons plays a key role in the formation of multiply charged ions. (C) 2004 Elsevier B.V. All rights reserved.

A fully integrated multi-channel detector for electron spectroscopy

Langstaff, David; Bushell, A.; Chase, T.; Evans, D.A., (2005) 'A fully integrated multi-channel detector for electron spectroscopy', Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 238 pp.219-223 RAE2008 Synchrotron Radiation in Materials Science ? Proceedings of the 4th Conference on Synchrotron Radiation in Materials Science 4th Conference on Synchrotron Radiation in Materials Science

Transition region, coronal heating and the fast solar wind

Li, Xing, 'Transition region, coronal heating and the fast solar wind', Astronomy and Astrophysics (2003) 406 pp.345-356 RAE2008

Plasma acceleration above Martian magnetic anomalies

Grande, Manuel, et al., 'Plasma acceleration above Martian magnetic anomalies', Science (2006) 311(5763) pp.980-983 RAE2008

Coronal loops heated by turbulence-driven Alfven waves

Li, Xing, Habbal, S. R., 'Coronal loops heated by turbulence-driven Alfven waves', The Astrophysical Journal, (2003) 598(2) pp.L125-L128 RAE2008

Dynamical Instabilities and Deterministic Chaos in Ballistic Electron Motion in Semiconductor Superlattices

We consider the motion of ballistic electrons within a superlattice miniband under the influence of an alternating electric field. We show that the interaction of electrons with the self-consistent electromagnetic field generated by the electron current may lead to the transition from regular to chaotic dynamics. We estimate the conditions for the experimental observation of this deterministic chaos and discuss the similarities of the superlattice system with the other condensed matter and quantum optical systems.