Ferrimagnetic and semiconducting CaCu3Fe2Sb2O12 by first principles

CaCu3Fe2Sb2O12 is mechanically stable, thermodynamically stable at pressures above 18 GPa. Both GGA and GGA + U methods predict that it is a ferrimagnetic semiconductor with Fe3+ in high spin state (S = 5/2). The coupling of Fe-Cu is antiferromagnetic, while that of Cu-Cu is ferromagnetic. The calculated total spin moment is 6.17 mu(B).

Covalent modification of a glassy carbon surface by 4-aminobenzoic acid and its application in fabrication of a polyoxometalates-consisting monolayer and multilayer films

4-Aminobenzoic acid (4-ABA) was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. X-ray photoelectron spectroscopy measurement proves the presence of 4-carboxylphenylamine monolayer on the GCE. The redox responses of various electroactive probes were investigated on the 4-ABA-modified GCE. Electron transfer to Fe(CN)(6)(3-) in solutions of various pHs was studied by both cyclic voltammetry and electrochemical impedance analysis on the modified electrode. Changes in the solution pH value result in the variation of the terminal group charge state, based on which surface pK(a) values are estimated. The 4-ABA-modified GCE was used as a suitable charged substrate to fabricate polyoxometalates-consisting (POM-consisting) monolayer and multilayer films through layer-by-layer assembly based on electrostatic attraction. Cyclic voltammetry shows the uniform growth of these three-dimensional multilayer films. Taking K10H3[Pr-(SiMo7W4O39)(2)]. H2O (abbreviated as Pr(SiMo7W4)(2)), for example, the preparation and electrochemical behavior of its monolayer and multilayer film had been investigated in detail. This modification strategy is proven to be a general one suitable for anchoring many kinds of POMs on the 4-ABA-modified GCE.

Gas-phase ion - Molecule reactions of neutral C-60 with the plasmas of alkyl methyl ethers and primary alcohols

The gas-phase ion-molecule reactions of C-60 with the methoxymethyl ion [CH3O=CH2](+) and the 1-hydroxyethyl ion [CH3CH=OH](+) generated under the self-chemical-ionization (self-CI) conditions of alkyl methyl ethers and primary alcohols were studied in the ion source of a mass spectrometer. The adduct ions [C60C2H5O](+) and protonated molecules [C60H](+) were observed as the major products of C-60 with the plasma of alkyl methyl ethers. On the contrary, the reactions of C-60 With the plasmas of primary alcohols produced few corresponding adduct ions. The AM1 semiempirical molecular orbital calculations were carried out on 14 possible structures. The calculated results showed that the most stable structure among the possible isomers of [C60C2H5O](+) is the [3+2] cycloadduct. According to experimental and theoretical results, the pathway for the formation of the adduct was presented.

Structures and vibrational spectra of C-2 and LaC2+ clusters

C-2 and LaC2+ were studied using Hartree-Fock(HF), B3LYP (Becke 3-paremeter-Lee-Yang-Parr) density functional method, second-order Moller-Plesset perturbation (MP2) and coupled cluster singles and doubles with non-iterative triples(CCSD(T)) methods. The basis set employed was LANL1DZ. Geometries, vibrational frequencies and other quantities were reported. The results showed that for C-2, all the methods performed well for low spin state (singlet), while only HF and B3LYP remained so for high spin state (triplet). For LaC2+, four isomers were presented and fully optimized. The results suggested that linear isomers with C-infinity v and D-infinity h symmetries were predicted to be saddle points on the energy surface for all the methods, while for isomers with C-2 upsilon and C-s symmetries, they were local minima except C-2 upsilon at B3LYP level, and were isoenergetic at HF, MP2 and CCSD(T) levels, near isoenergetic at B3LYP level. From the differences between HOMO and LUMO, it is also known that the isomers with C-2 upsilon and C-s symmetries offer the largest values and therefore correspond to the most stable structure. For La-C bond lengths, B3LYP gives the shortest, the order is B3LYP

MAGNETIC-PROPERTIES OF LANTHANUM MANGANITE AND VALENCE EQUILIBRIA OF MANGANESE

The paramagnetic susceptibility of lanthanum manganite has been measured over a wide temperature range (100-1073 K). On the basis of the thermodynamic equilibria between the various manganese ions with different valence and spin states and the magnetic interactions between the various manganese ions, a semiempirical formula has been proposed to calculate the paramagnetic susceptibilities of lanthanum manganite at different temperatures. The results indicate that most of the discrepancies between the calculated and experimental reciprocal susceptibilities of lanthanum manganite are less than 10% and that the relative contents of the various manganese ions in lanthanum manganite vary with temperature. The relative content of the trivalent manganese ion with a high spin state is dominant over the whole temperature range, while be relative content of the tetravalent manganese ion with a high spin state decreases monotonously with increasing temperature. At 300 K the calculated relative content of the tetravalent manganese ion in lanthanum manganite is about 34%, which is in good agreement with the experimental result (30%). There are some divalent manganese ions present in lanthanum manganite from low temperature to high temperature. The ratio of the relative contents of the tetravalent and divalent manganese ions in the compound varies with temperature. Above 750 K the relative content of the tetravalent manganese ion is less than that of the divalent manganese ion. The variation in the electrical resistivity of lanthanum manganite with temperature has also been interpreted reasonably.

STUDY ON BONDING AND 4F ORBITAL EFFECT OF LANTHANIDE COMPOUNDS

The bonding and the 4f orbital effect of lanthanide elements at different valence state in their compounds have been studied by INDO method in this paper. The results obtained show that the bonding of lanthanide compounds is affected by many factors, such as valence state, ionic radius, ligand, coordinate number, space configuration etc. The strength of bonds composed of different ligands with lanthanide is distinctly different. The covalence of Ln-L bonds of lanthanide ions at high valence state in their compounds is larger than that at low valence state, The covalency at low coordinate number is larger than that at high coordinate number. Some lanthanide compounds with special configuration, besides sigma-bond, can form p(pi)-d(pi) dative bond with much overlap, which makes the Ln-L bond increase markedly. The effect of 4f orbitals on bonding is far less than that of 5d orbitals. The Ln 4f orbitals at 3 or 2 valence state may be considered to be essentially localized, while the contribution of 4f orbitals on bonding in 4 valent cerium compounds increases obviously, up to 1%.

ELECTROCHEMICAL TRANSFER OF 12-SILICOTUNGSTATE ANION ACROSS THE WATER NITROBENZENE INTERFACE

It has been firstly found by means of cyclic voltammetry (CV) and chronopotentiometry with linear current-scanning (CLC)that 12-silicotungstate anion (SiW_(12)O_(40)~(4-)) with high charge numbers, large molecular volume and symmetric structure can cross

Methane aromatization in the absence of an added oxidant and the bench scale reaction test

A bench scale reaction test for methane aromatization in the absence of an added oxidant was performed and its reaction result evaluated based on the carbon balance of the system. The result was compared with those obtained from the micro-reaction test to ensure the accuracy of the internal standard analyzing method employed in this paper. The catalytic performances of modified Mo/HZSM-5 catalysts were examined. It was found that pre-treatment by steam on HZSM-5 weakened the serious deposition of coke, and pre-impregnation of n-ethyl silicate on HZSM-5 could improve the conversion of CH4, but had little effect on coke formation. A low temperature activation procedure including pre-reduction of the catalyst with methane prevents the zeolite lattice from being seriously destroyed by high valence state Mo species when the Mo loading is high. It was suggested that Mo2C species detected by XRD spectra was the active phase for CH4 aromatization.

Fermi-Level Pinning at Metal/High-k Interface Influenced by Electron State Density of Metal Gate

The Fermi-level pinning (FLP) at the metal/high-k interface and its dependence on the electron state density of the metal gate are investigated. It is found that the FLP is largely determined by the distortion of the vacuum level of the metal which is quantitatively ruled by the electron state density of the metal. The physical origin of the vacuum level distortion of the metal is attributed to an image charge of the interface charge in the metal. Such results indicate that the effective work function of the metal/high-k stack is also governed by the electron state density of the metal.

HIGH-TEMPERATURE SUPERCONDUCTOR, YBA2CU3O7-X AS ALL-SOLID-STATE LITHIUM CELL

The utility of the high-temperature superconductor, YBa2Cu3O7-x as the cathode material for an all-solid-state lithium cell has been examined. The capacity of YBa2Cu3O7-x is 223 mA h g-1 and the discharge efficiency is > 92%. Measurements of a.c. impedance show that the charge-transfer resistance at the interface of the electrolyte/cathode is very low and increases with the depth-of-discharge of the battery. Studies using X-ray photoelectron spectroscopy (XPS) reveal that the cathode becomes doped with Li+ ions as the cell discharges.

Numerical Analysis of the Effects of Free-Stream Thermo-Chemical State on the Test Model Flow Field in High-Enthalpy Tunnel

The effects of the free-stream thermo-chemical state on the test model flow field in the high-enthalpy tunnel are studied numerically. The properties of the free-stream, which is in thermo-chemical non-equilibrium, are determined by calculating the nozzle flow field. A free-stream with total enthalpy equal to the real one in the tunnel while in thermo-chemical equilibrium is constructed artificially to simulate the natural atmosphere condition. The flow fields over the test models (blunt cone and Apollo command capsule model) under both the non-equilibrium and the virtual equilibrium free-stream conditions are calculated. By comparing the properties including pressure, temperature, species concentration and radiation distributions of these two types of flow fields, the effects of the non-equilibrium state of the free-stream in the high-enthalpy shock tunnel are analyzed.

A Q-swicthed all-solid-state single-longitudinal-mode laser with adjustable pulse-width and high repetition rate

A single-longitudinal-mode (SLM) laser-diode pumped Nd: YAG laser with adjustable pulse width is developed by using the techniques of pre-lasing and changing polarization of birefingent crystal. The Q-switching voltage is triggered by the peak of the pre-lasing pulse to achieve the higher stability of output pulse energy. The output energy of more than 1 mJ is obtained with output energy stability of 3% (rms) at 100 Hz. The pulse-width can be adjusted from 30 ns to 300 ns by changing the Q-switching voltage. The probability of putting out single-longitudinal-mode pulses is almost 100%. The laser can be run over four hours continually without mode hopping.

First-principles study of ground-state properties and high pressure behavior of ThO2

The mechanical properties, electronic structure and phonon dispersion of ground state ThO2 as well as the structure behavior up to 240 GPa are studied using first-principles density-functional theory. Our calculated elastic constants indicate that both the ground-state fluorite structure and high pressure cotunnite structure of ThO2 are mechanically stable. The bulk modulus, shear modulus, and Young's modulus of cotunnite ThO2 are all smaller by approximately 25% compared with those of fluorite ThO2. The Poisson's ratios of both structures are approximately equal to 0.3 and the hardness of fluorite ThO2 is 22.4 GPa. The electronic structure and bonding nature of fluorite ThO2 are fully analyzed, and show that the Th-O bond displays a mixed ionic/covalent character. The phase transition from the fluorite to cotunnite structure is calculated to occur at the pressure of 26.5 GPa, consistent with recent experimental measurement by ldiri et al. [1]. For the cotunnite phase it is further predicted that an isostructural transition takes place in the pressure region of 80-130 GPa.

Reduced dynamics with renormalization in solid-state charge qubit measurement

Quantum measurement will inevitably cause backaction on the measured system, resulting in the well-known dephasing and relaxation. In this paper, in the context of solid-state qubit measurement by a mesoscopic detector, we show that an alternative backaction known as renormalization is important under some circumstances. This effect is largely overlooked in the theory of quantum measurement.