Electronic properties and stabilities of methoxy-substituted Lindqvist polyoxometalates [Nb<Subscript>2</Subscript>W<Subscript>4</Subscript>O<Subscript>19</Subscript>CH<Subscript>3</Subscript>]<Superscript>3−</Superscript> by DFT

The electronic properties and stabilities of five [Nb₂W₄O₁₈OCH₃]³⁻ isomers have been investigated using a density functional theory method. The results show that the isomer with the methoxy group occupying a bridging position between two tungsten atoms (two tungsten atoms in the plane that contains two niobium atoms) in the [Nb₂W₄O₁₈OCH₃]3⁻ framework is the most stable isomer in acetonitrile. The stability of the one-electron-reduced isomers changes little. The most stable one-electron-reduced isomer has the methoxy group occupying a bridging position between niobium atoms in the [Nb₂W₄O₁₈OCH₃]⁴⁻ framework. The M-Ob (M = Nb, W; b denotes bridging) bond lengths in anions in which the metal atoms are connected by a methoxy group are longer than those in [Nb₂W₄O₁₉]⁴⁻. The highest occupied molecular orbitals (HOMO) in [Nb₂W₄O₁₉]⁴⁻ mainly delocalize over the bridging oxygen atoms of two niobium atoms and two tungsten atoms located in the equatorial plane, and the bridging oxygen atoms on the axial surface. The lowest unoccupied molecular orbitals (LUMO) of [Nb₂W₄O₁₉]⁴⁻ are mainly concentrated on the tungsten atoms and antibonding oxygen atoms. Methoxy substitution modifies the electronic properties of the [Nb₂W₄O₁₈OCH₃]³⁻ isomers. The HOMOs in the five isomers formally delocalize over the bridging oxygen atoms, which are distant from the surface containing the methoxy group and four metal atoms. The LUMOs delocalize over the d-shells of the four metal atoms that are close to the methoxy group, and the p-orbitals of oxygen. One-electron reduction occurred at the tungsten atoms, not the niobium atoms.     

A phase field study for influence of elastic energy on L1<Subscript>0</Subscript>→L1<Subscript>2</Subscript> transient ordering in Ni<Subscript>75</Subscript>Al<Subscript>17</Subscript>Zn<Subscript>8</Subscript>

The influence of the elastic energy on L1₀→L1₂ transient ordering transformation was investigated by microscopic phase field method. It is found that there are three stages experienced in atomic ordering: solute clustering+L10 short range ordering → L1₀ long range ordering → L1₂ long range ordering. Before the formation of the high ordered L1₂ phase, it has firstly taken place the transformation from matrix to L1₀ phase, and then held the L1₀→L1₂ secondary transformation. Elastic energy is proved to take little effect on the stage of short range ordering, but as the elastic energy is multiplied, it obviously shortened the course of the solute clustering, and speeded up the proceeding of the L1₀ long range ordering transition. Accordingly, the increased elastic energy also strengthens the single crystalline directionality of L1₀ phase projecting on 2D plane and makes the ordered degree of Al and Zn atoms enhanced. With the temperature elevation, Al’s and Zn’s ordered degree decreased in L10 phase.     

Research on effects of hydrostatic pressure on the dielectric property of Pb(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3−</Subscript>BaTiO<Subscript>3−</Subscript> PbTiO<Subscript>3</Subscript> relaxor ferroelectric ceramics

The dielectric properties of Pb(Zn1_1/3Nb_2/3)O₃₋ BaTiO₃₋PbTiO₃ relaxor ferroelectric ceramics near the rhombohedral and tetragonal phase boundary were investigated under hydrostatic pressure. It was found that hydrostatic pressure made their phase transition temperature T _c and the peak temperature T _m decreased, and the frequency dispersion and relaxor behavior enhanced. In these disorder systems of composite pervoskite structures, there appeared polar clusters or nanodomains. The unique physical characteristics, which made the relaxor behavior enhanced, is that the correlation length among these nanodomains decreases greatly with the pressure increasing.     

Regional Δ<Superscript>14</Superscript>C patterns and fossil fuel derived CO<Subscript>2</Subscript> distribution in the Beijing area using annual plants

The level of atmosphericΔ14C and the fossil fuel derived CO 2 concentration in the Beijing area from May to September,2009, were systematically analyzed based on radiocarbon(14C)measurements of annual plants by accelerator mass spectrometry(AMS). The results show that the maximumΔ14C in Beijing was 29.6‰±2.2‰,and the minimum was–28.2‰±2.5‰,with a trend of decreasingΔ14C from the outer suburbs to inner suburbs to the urban center.This trend correlates well with increases in fossil fuel derived CO2 caused by human activities such as population density,industrial emissions and traffic,with lower values of atmosphericΔ14C associated with more intensive human activities.The fossil fuel derived CO 2 concentrations from May to September, 2009,ranged from 3.9±1.0 ppm to 25.4±1.0 ppm.It was calculated that each additional 1 ppm of CO2 from fossil fuels depleted the atmosphericΔ14C by approximately 2.70‰.This study suggests that 14C measurements of annual plants by AMS provide an effective method to rapidly trace fossil fuel derived CO2.     

Crystal structure and negative thermal expansion of solid solution Lu<Subscript>2</Subscript>W<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>12</Subscript>

A new series of solid solutions Lu₂W_3−x Mo _x O₁₂ (0.5≤x≤2.5) were successfully synthesized by the solid-state method. Their crystal structure and negative thermal expansion properties were studied using high-temperature X-ray powder diffraction and the Rietveld method. All samples of rare-earth tungstates and molybdates are found to crystallize in the same orthorhombic structure with space group Pnca and show the negative thermal expansion phenomena related to transverse vibration of bridging oxygen atoms in the structure. Thermal expansion coefficients (TEC) of Lu₂W_3−x Mo _x O₁₂ are determined as −20.0×10⁻⁶ K⁻¹ for x=0.5 and −16.1×10⁻⁶ K⁻¹ for x=2.5 but -18.6×10⁻⁶ and −16.9×10⁻⁶ K⁻¹ for unsubstituted Lu₂W₃O₁₂ and Lu₂Mo₃O₁₂ in the identical temperature range of 200 to 800°C. High-temperature X-ray diffraction (XRD) data and bond length analysis suggest that the difference between W-O and Mo-O bond is responsible for the change of TECs after the element substitution in this series of solid solutions.     

Preparation and thermal stability of Pd<Subscript>40.5</Subscript>Ni<Subscript>40.5</Subscript>Si<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>P<Subscript>19−<Emphasis Type="Italic">x</Emphasis></Subscript> bulk metallic glasses

With the addition of Si to replace some P, Pd_40.5Ni_40.5Si _x P_19−x (x=0, 2.5, 5, 9.5, 14, and 19 in atomic number fraction) bulk glassy samples with the diameter of about 5 mm were successfully prepared by use of flux treatment and water quenching technology. With the increase of Si content, the glass forming ability of Pd_40.5Ni_40.5Si _x P_19−x increases first for low Si content and then decreases for high Si content (Si≥9.5at%). The Pd_40.5Ni_40.5Si ₅ P₁₄ glassy alloy possesses the largest supercooled liquid region ΔT of 119 K, the largest reduced glass transition temperature of 0.621, and the largest γ parameter of 0.460, indicating that this glassy alloy possesses very large glass forming ability and very high thermal stability.     

Synthesis of γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript>/Au magnetic composites for immobilization of bovine serum albumin

A method for the two-step synthesis of magnetic composites with a γ-Fe₂O₃ core, silica inner layer and numerous gold nanoparticles supported on the surface of the silica (γ-Fe₂O₃/SiO₂/Au) is described. First, thiol-functionalized γ-Fe₂O₃/SiO₂ composites and gold colloids are prepared by modifying γ-Fe₂O₃/SiO₂ composites with mercaptosilane and reduction of Au³⁺ to Au⁰ with citrate, respectively. Gold nanoparticles are then assembled on the surface of the thiol-functionalized γ-Fe₂O₃/SiO₂ composites to form γFe₂O₃/SiO₂/Au composites. The structure of the composite particles is confirmed by transmission electronic microscopy and powder X-ray diffraction. Immobilization studies with bovine serum albumin (BSA) demonstrate that the γ-Fe₂O₃/SiO₂/Au composites can be used to immobilize BSA, making them useful for biomedical and biological applications.     

First principles studies on the electronics structures of (Li<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Me<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)FePO<Subscript>4</Subscript> (Me=Na and Be)

Based on density functional theory (DFT) of the first-principle for cathode materials of lithium ion battery, the electronic structures of (Li_1?x Me _x )FePO₄ (Me=Na and Be, x=0–0.40) are calculated by plane wave pseudo-potential method using Cambridge serial total energy package (CASTEP) program. The calculated results show that Li-site doping can improve the electronic conductivity enormously. Doping with Na has a noticeable effect on improving its electrical conductivity. However, serious structural distortion will occur when its doping density is beyond 0.25. In view of this, the best density of doping Na is less than 0.25. Doping with Be has an inconspicuous effect on increasing its electrical conductivity and has good cyclical stability, but it cannot achieve as good results as when it is doped with Na. Therefore we cannot find a middle ground between the two proposals. Considering cost and environmental protection, it is ideal to choose Na. So this method gives a reasonable prediction to the improvement of electronic conductivity through Li-site doping in LiFePO₄ material.     

Modification of MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript> spinel inclusions in Al-killed steel by Ca-treatment

The modification of MgO·Al₂O₃ spinel inclusions in Al-killed steel by Ca-treatment has been studied by industrial trials and thermodynamic calculations. In the industrial trials, samples were taken systematically during the refining process in which the molten steel was treated by calcium, and the characters of the inclusions were analyzed using scanning electron microscopy (SEM) and energy dispersive spectra (EDS). The effects of Ca-treatment were evaluated by tracking the compositions of the inclusions. The results show that the modification of MgO·Al₂O₃ spinel inclusions by Ca-treatment is effective and the transformation sequence of the inclusions during the refining is Al₂O₃→MgO·Al₂O₃→liquid complex inclusions. The modification of spinel inclusions by Ca-treatment was calculated by FactSage6.0 utilizing its free-energy minimization routines. The results of thermodynamic calculations indicate that spinel inclusions are easier to be modified than Al₂O₃ inclusions and the spinel inclusions in 30CrMo steel would transform to liquid complex inclusions when the content of dissolved Ca in the molten steel exceeds 1×10⁻⁶. Also, the results show that adding more calcium into the molten steel would lower the contents of Al₂O₃ and MgO and increase the CaO content of the inclusions, while the change in SiO₂ content is little.     

Thermodynamic analysis on the formation mechanism of MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript> spinel type inclusions in casing steel

MgO·Al₂O₃ spinel type inclusions in casing steel were analyzed by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS). The results show that there are three forms. One is pure MgO·Al₂O₃ spinel, another is the composite oxide of the Mg-Al-Ca-Si-O system, and the third is the complex with oxide as a core covered by sulfide. The formation mechanisms were studied. The influences of slag basicity and vacuum degree on the magnesium content during the vacuum treatment of molten steel and furnace lining in molten steel were calculated with the coexistence theory of slag structure. The results show that the magnesium content increases with the increase in slag basicity and aluminum content in molten steel, and decreases with the increase in CO partial pressure.     

Effect of Mg content on the structural and optical properties of Mg<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>O alloys

Mgx Zn1–x O thin films with x = 0, 0.11, 0.28, 0.44, 0.51, and 0.65 were grown by plasma-assisted molecular beam epitaxy on (0001) sapphire substrates. X-ray diffraction measurement reveals that phase separation of the Mgx Zn1–x O films occurred at x =0.44 and 0.51. Optical absorption spectra show that the absorption edges of the films shift to high-energy side with increasing Mg contents. In resonant Raman spectra, multiple-order Raman peaks originating from ZnO-like longitudinal optical phonons were obser...     

Is pedogenic carbonate an important atmospheric CO<Subscript>2</Subscript> sink?

Nearly 18 years after the proposal of the weathering-related carbon sink concept(Berner R A.Weathering,plants and the long-term carbon cycle.Geochim Cosmochim Acta,1992,56:3225-3231),it is an appropriate timing to re-evaluate its geological context with the updated dataset.Ryskov et al.(Ryskov Ya G,Demkin V A,Oleynik S A,et al.Dynamics of pedogenic carbonate for the last 5000 years and its role as a buffer reservoir for atmospheric carbon dioxide in soils of Russia.Glob Planet Change,2008,61:63-69) lately c...     

Structural dependences of the <Emphasis Type="Italic">η</Emphasis><Superscript>6</Superscript> complexes of 3-amino-9-ethylcarbazole with chromium tricarbonyl fragment on third-order optical nonlinearities

Degenerate four-wave mixing measurements, using the 35 ps pulses at 532 nm, have been employed to investigate the third-order nonlinear optical parameters of two chromium tricarbonyl complexes η6-bonded to 3-amino-9-ethylcarbazole at either the NH2-substituted aryl ring （1） or the unsubstituted ring （2） and their precursor 3-amino-9-ethylcarbazole （AECz）. The second-order hyperpolarizability y of the compounds 1 and 2 were found to be 42.9×10^-31 and 35.9×10^-31 esu, respectively, approximately one order of magnitude greater than AECz. The relation between the molecular structure and second-order hyperpolarizability of the compounds I and 2 was explored in detail based on the three-level model and the density functional theory （DFT） calculation. The theoretical results indicate that the spatial distribution of electron density has the profound role in the third-order nonlinear optical properties.     

Fatty-acids and their <Emphasis Type="Italic">δ</Emphasis><Superscript>13</Superscript>C characteristics of seep carbonates from the northern continental slope of Gulf of Mexico

Here we reported the fatty-acids and their δ¹³C values in seep carbonates collected from Green Canyon lease block 185 (GC 185; Sample GC-F) at upper continental slope (water depth: ~540 m), and Alaminos Canyon lease block 645 (GC 645; Sample AC-E) at lower continental slope (water depth: ~2200 m) of the Gulf of Mexico. More than thirty kinds of fatty acids were detected in both samples. These fatty acids are maximized at C₁₆. There is a clear even-over-odd carbon number predominance in carbon number range. The fatty acids are mainly composed of n-fatty acids, iso-/anteiso-fatty acids and terminally branched odd-numbered fatty acids (iso/anteiso). The low δ¹³C values (−39.99‰ to −32.36‰) of n-C₁₂:0, n-C₁₃:0, i-C₁₄:0 and n-C₁₄:0 suggest that they may relate to the chemosynthetic communities at seep sites. The unsaturated fatty acids n-C_18:2 and C_18:1△⁹ have the same δ¹³C values, they may originate from the Beggiatoa/Thioploca. Unlike other fatty acids, the terminally branched fatty acids (iso/anteiso) show lower δ¹³C values (as low as −63.95‰) suggesting a possible relationship to sulfate reducing bacteria, which is common during anaerobic oxidation of methane at seep sites.     

Distribution of <Emphasis Type="Italic">δ</Emphasis><Superscript>18</Superscript>O in surface snow along a transect from Zhongshan Station to Dome A,East Antarctica

Surface snow samples were collected during the 14th (1997/1998) and 24th (2007/2008) Chinese National Antarctica Research Expeditions along a transect from Zhongshan Station to Dome A. The stable oxygen isotope ratios of these samples were measured to investigate their relationships with temperature and geographical parameters (latitude, longitude, altitude and distance to the coast). The results reveal a strong positive correlation (R=0.945) between δ¹⁸O and mean annual temperature, with a gradient of 0.84‰°C ^–1, which is a little higher than that in Terre Adelie Land. Regression analyses also show that the δ¹⁸O of surface snow is strongly correlated with distance to the coast (R=0.942), latitude (R=0.942), and altitude (R=0.941). But no significant correlation was found between δ¹⁸O and longitude in study area. Altitude should be the most important factor influencing the δ¹⁸O distribution because of distinctive topography. The δ¹⁸O-altitude and T-altitude gradients along this transect are determined to be –1.1‰/100 m and 1.31°C/100 m, respectively.     

Second organic aerosol formation by irradiation of α-pinene-NO<Subscript>x</Subscript>-H<Subscript>2</Subscript>O in an indoor smog chamber for atmospheric chemistry and physics

Ozone（O3） and secondary organic aerosol （SOA） are considered to be the most serious secondary air pollutants of concern in most metropolitan areas, as well as for Beijing. In this study, 03 and SOA formation potential of α-pinene, the most abundant biogenic VOCs, is investigated at Tsinghua Indoor Chamber Facility. The experiments were conducted under atmospheric relevant HCs/NOx ratios in both presence and absence of ammonia sulfate seed aerosol. A Scanning Mobility Particle Sizer system （3936, TSI） and a Condensation Particle Counter （3010, TSI） were used to study the SOA formation and a gas chromatograph （GC） equipped with a DB-5 column and a flame ionization detector （FID） was used to measure α-pinene simultaneously. The results show that the presence of ammonia sulfate seed aerosol did not change the formation trend of 03, but significantly contribute to SOA formation. A strong linear relationship （r^2 = 0.90） between SOA yield enhancement （△Y＊） and surface concentration of seed aerosol （PM1, s）has been found, denoting that the PMi, s is the control factor for SOA yield enhancement. And the possible reason for the enhancement is acid-catalyzed heterogeneous reactions.     

Preliminary results of TiO<Subscript>2</Subscript> mapping using Imaging Interferometer data from Chang’E-1

The distribution of titanium abundance on the lunar surface is important knowledge for lunar geologic studies and future resource utilization.In this paper,we develop a preliminary model based on"ground truths"from Apollo and Luna sample-return sites to produce a titanium abundance map from Chang’E-1 Imaging Interferometer(IIM) images.The derived TiO2 abundances are validated with Clementine UVVIS results in several regions,including lunar highlands neighboring the Apollo 16 landing site,and high-Ti and low-Ti maria near the standard site of Mare Serenitatis(MS2) .The validation results show that TiO2 abundances modeled with Chang’E-1 IIM data are overestimated for highlands(～0.7 wt.%) and low-Ti maria(～1.5 wt.%) and underestimated for high-Ti maria(～0.8 wt.%).     

δD values of escaped H<Subscript>2</Subscript> from hot springs at the Tengchong Rehai geothermal area and its origin

Here we give the · values of escaped H₂ from hot springs at the Tengchong Rehai and adjacent regions, and deal with a genetic correlation between the increment H₂ in escaped gases from middle-shallow reservoirs and the H₂S, CH₄ derived from deep sources. Isotopic compositions of H₂ indicate that the generation of increment H₂ may be related to recent strong activity of N-W trending fault at the Rehai area. Trace monitoring the H₂ release could be significant in order to keep watch on present activity ofthat fault.     

Atomic decomposition in L p (ℝ n ) (1 <p < 2)

An atomic decomposition in L^p ( 1 <p < 2) with tent space is given.     

<Emphasis Type="Italic">a</Emphasis>-Wythoff’s game with <Emphasis Type="Italic">n</Emphasis> players

Letting a = 1 in a- Wythoff’s game introduced by Fraenkel yields Wythoff’s game which is a well-known 2-player impartial combinatorial game introduced by Wythoff in 1907. A method of solving n-player impartial games was presented by Krawec in 2012. In this paper, we employ Krawec’s function to analyze n > 2 players a-Wythoff’s game and obtain game values for all a 1. The results obtained cover n-player Wythoff’s game, a special case 1-Wythoff’s game.