Electronic structure studies of Mg0.95Mn0.05Fe2−2xTi2xO4 (0x0.8)

The electronic structure of Mg_0.95Mn_0.05Fe_2−2xTi_2xO₄ (0x0.8) compound is investigated using near edge X-ray absorption fine structure, (NEXAFS) spectroscopy measurements, carried out at O K, Fe and Ti L_3,2-edges at room temperature. The O K-edge spectra indicate that the Fe 3d orbitals have been considerably modified and a new spectral feature start dominating in the pre-edge region at higher Ti doping. The Fe 2p NEXAFS spectra exhibit a mixed valent Fe²⁺/Fe³⁺ states apart from the conversion of Fe³⁺ to Fe²⁺ with the substitution of Ti ions. The Ti L_3,2-edge spectra indicate that Ti ions remain unchanged at 4+ state. These variations in the host electronic structure due to Ti substitution are consistent with the dielectric and transport properties of the material.     

CO$lt;sub$gt;2$lt;/sub$gt;激光烧结合成负热膨胀材料Sc$lt;sub$gt;2$lt;/sub$gt;($lt;i$gt;M$lt;/i$gt;O$lt;sub$gt;4$lt;/sub$gt;)$lt;sub$gt;3$lt;/sub$gt;($lt;i$gt;M$lt;/i$gt;=W,Mo)及其拉曼光谱

用CO₂激光烧结合成了负热膨胀材料Sc₂(WO₄)₃和Sc₂(MoO₄)₃. 实验表明, 激光合成负热膨胀材料Sc₂(WO₄)₃和Sc₂(MoO₄)₃属于快速合成技术, 合成一个样品的时间仅需几秒到十几秒, 具有快速凝固的特征; X射线衍射和拉曼光谱分析表明, 所合成的材料为正交相结构, 且具有较高的纯度; 变温拉曼光谱分析表明, 所合成的材料在室温以上没有相变, 但可能有微弱的吸水性; 在对Sc₂O₃, MoO₃, WO₃, Sc₂(MoO₄)₃和Sc₂(WO₄)₃拉曼光谱分析的基础上, 给出了激光光子能量及原料和合成产物的声子能级图, 分析了激光烧结合成的机理. 激光光子能量转化为激发声子的能量是光热转化的主要通道, 原料在熔池中反应并快速凝固形成最终产物. 关键词： 负热膨胀材料 合成 激光烧结 拉曼光谱     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

超冷铯分子0u+(6P3/2)长程态的高灵敏光缔合光谱研究

利用发展的调制俘获损耗荧光光谱技术实验测量了超冷铯分子0_u⁺(6P_3/2)长程态的高灵敏光缔合光谱. 光谱探测范围较国际已有报道扩大了60 cm^-1, 观察到25个长程区域新的振动能级. 通过LeRoy-Bernstein公式对振动束缚能数据进行拟合, 获得了超冷铯分子0_u⁺(6P_3/2)态的长程系数C₃ 为16.103±0.010. 构建了超冷铯分子0_u⁺(6P_3/2)态长程区域的势能曲线.     

Band analysis of the Swan system (dΠg-aΠu) of C2 and CC molecules

The emission spectrum of the d³Π_g-a³Π_u system (Swan bands) due to ¹³C₂ and ¹²C¹³C molecules has been obtained in a low pressure hollow cathode discharge through a mixture of argon and benzene containing enriched ¹³C (90%). The spectrum was photographed on a 3.4-m Ebert spectrograph (reciprocal dispersion 0.54 Å mm⁻¹ in the first order). Isotope effect measurements have been carried out to determine the shift between isotopic bands and those emitted by ordinary molecules. The rotational analysis of six ¹³C₂ bands and three bands of ¹²C¹³C has been performed and molecular constants were derived.     

Magneto-optical study of slanted Co nanowires embedded in CeO2/SrTiO3(0 0 1)

Sequential pulsed laser deposition of CoO and CeO₂ at 650 °C under vacuum leads to the formation of a slanted Co nanowires assembly embedded in CeO₂/SrTiO₃(0 0 1) epilayers. High temperature magneto-optical Faraday measurements were performed, which revealed a Faraday ellipticity of 1.3° at a wavelength of 450 nm for 300 nm thick samples and which allowed to access the magnetic properties. From the analysis of the coercivity dependence on temperature, it is shown that the magnetic anisotropy of the slanted Co nanowires is dominated by shape anisotropy and that their magnetization reversal is localized.     

The ν2+ν4 Band of Carbonyl Fluoride

We have measured and fitted over 600 lines in the ν₂+ν₄ combination band of COF₂. The spectrum is well reproduced by extrapolation of rotational constants from the ν₂ and ν₄ fundamentals, with no evidence of significant perturbation. The band centre of 2195.272 15(11) cm⁻¹ permits an estimate of −11.32 cm⁻¹ for the anharmonicity constant x₂₄.     

Hydroxylated α-Al2O3 (0 0 0 1) surfaces and metal/α-Al2O3 (0 0 0 1) interfaces

X-ray photoelectron spectroscopy was applied to study the hydroxylation of α-Al₂O₃ (0 0 0 1) surfaces and the stability of surface OH groups. The evolution of interfacial chemistry of the α-Al₂O₃ (0 0 0 1) surfaces and metal/α-Al₂O₃ (0 0 0 1) interfaces are well illustrated via modifications of the surface O1s spectra. Clean hydroxylated surfaces are obtained through water- and oxygen plasma treatment at room temperature. The surface OH groups of the hydroxylated surface are very sensitive to electron beam illumination, Ar⁺ sputtering, UHV heating, and adsorption of reactive metals. The transformation of a hydroxylated surface to an Al-terminated surface occurs by high temperature annealing or Al deposition.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

MEASUREMENT OF HYPERFINE COUPLING CONSTANTS OF THE EXCITED STATES 4f7(8S07/2)6p3/2(7/2, 3/2) IN 151,153Eu+

Hyperfine structure spectra of singly ionized europium have been measured by collinear fast-ion-beam laser spectroscopy. All the spectral lines were resolved and the magnetic dipole and electric quadrupole coupling constants of the metastable and excited levels were determined.     

利用双光缔合光谱技术直接测量超冷铯分子0u+(6S1/2+6P1/2)长程态的转动常数的实验研究

实验获得了超冷铯分子6S_1/2+6P_1/2离解限下0_u⁺长程态振动能级v=187的转动常数. 首先利用调制的荧光光谱技术获得了高分辨的转动量子数J=0–6的超冷铯分子纯转动光谱. 利用双光缔合光谱技术, 构建了高精度的频率参考信号, 进而得到了相邻转动能级间的频率间隔. 最后通过非刚性转子模型拟合得到了转动常数和离心畸变常数.     

Electron surface states in short-period superlattices: (GaAs)2/(AlAs)2(1 0 0)-c(4 × 4)

The electronic structure of (GaAs)₂/(AlAs)₂(1 0 0)-c(4 × 4) superlattice surfaces was studied by means of angular-resolved photoelectron spectroscopy (ARUPS) in the photon energy range 20-38 eV. Four samples with different surface termination layers were grown and As-capped by molecular beam epitaxy (MBE). ARUPS measurements were performed on decapped samples with perfect c(4 × 4) reconstructed surfaces. An intensive surface state was, for the first time, observed below the top of the valence band. This surface state was found to shift with superlattices’ different surface termination in agreement with theoretical predictions.     

Argon ion laser-induced BaS BΣ-AΣ, A′Π, aΠ, and XΣ fluorescence spectra: Analysis of A A′, A a, and A′ a perturbations

The 333.6-, 351.1-, and 363.8-nm lines of a cw argon ion laser are found to coincide with the BaS B¹Σ⁺-X¹Σ⁺ (12, 0) R(17), (6, 0) P(35), and (3, 0) R(125) transitions, respectively. Fluorescence transitions from the laser-prepared upper levels terminating in X¹Σ⁺ V = 0–28, A¹Σ⁺ V = 1–3, A′¹Π V = 1–13, and a³Π₁ V = 3–12 are assigned. These results are combined with a previous analysis of the extensively perturbed BaS A¹Σ⁺-X¹Σ⁺ system [R. F. Barrow, W. G. Burton, and P. A. Jones, Trans. Farad. Soc.67, 902–906 (1971)]. Every observed perturbation of the BaS A¹Σ⁺ state is electronically and vibrationally assigned. The levels a³Π₀ V = 10–13, a³Π₁ V = 12–14, a³Π₂ V = 15, and A′¹Π V = 10–13 are sampled via their perturbations of A¹Σ⁺ V = 0–2. Although the mutual interactions of the a³Π, A′¹Π, and A¹Σ⁺ states approach Hund's case (c) limit, a complete deperturbation is performed from a case (a) starting point. Of the five lowest energy electronic states of BaS, only b³Σ⁺ remains uncharacterized. Principal deperturbed molecular constants are (in cm⁻¹, 1σ uncertainties in parentheses):

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High-precision frequency measurements of the ν1 + ν3 combination band of C2H2 in the 1.5 μm region

A pair of 1.5 μm semiconductor laser frequency standards have been developed for optical telecommunications use, stabilised to transitions of ¹²C₂H₂ and ¹³C₂H₂, using cavity-enhanced Doppler-free saturation absorption spectroscopy. The absolute frequencies of 41 lines of the ν₁ + ν₃ band of ¹²C₂H₂, covering the spectral region 1520-1545 nm, have been measured by use of a passive optical frequency comb generator, referenced to ¹³C₂H₂ transitions of known frequency. The mean experimental uncertainties (coverage factor k = 1) of the frequency values are 3.0 kHz (type A) and 10 kHz (type B). Improved values of the band origin ν₀, rotational constants B′ and B″, and centrifugal distortion coefficients D′, D″, H′, and H″ are presented.     

Mössbauer spectroscopic studies of the disintegration of hexavalent iron compounds (BaFeO4 and K2FeO4)

Mössbauer spectroscopic studies of BaFeO₄ and K₂FeO₄ as prepared, then either sealed, or exposed to air, or exposed to moist air for a period up to more than one year, were performed at room temperature as a function of time. Some of the samples were studied as a function of temperature down to 4.2 K. K₂FeO₄ and BaFeO₄ after preparation, exhibit a pure Fe⁶⁺ spectrum. K₂FeO₄ shows low stability. After a period of 14 months in a sealed sample holder, the spectrum exhibits 83% noncrystalline Fe³⁺, as Fe₂O₃ nanoparticles, and only 17% of the original Fe⁶⁺. BaFeO₄ sealed, or exposed to dry air disintegrates slowly, exhibiting a spectrum composed of three subspectra. In addition to the original Fe⁶⁺ and final Fe³⁺ subspectra, a subspectrum, of an intermediate stage of a crystalline Fe⁴⁺ system, is present. In the first month the increase of the Fe³⁺ subspectrum is 15%, and that of the Fe⁴⁺ is 8%. BaFeO₄ exposed to moist air, disintegrates at a very fast rate. The Fe³⁺ subspectrum, due to Fe₂O₃ nanoparticles, increases in the first days at the rapid rate of ∼13%/day, and there is no evidence for Fe⁴⁺ in the spectrum. The Fe⁶⁺ in BaFeO₄, Fe³⁺ and Fe⁴⁺ in the disintegrated systems are all magnetically ordered at 4.2 K. Above 90 K the Fe³⁺ subspectra exhibit a superposition of a paramagnetic doublet and a diffuse magnetic sextet, with relative intensities changing with temperature, and changing from sample to sample according to their blocking temperatures, which are determined by the distribution in size of the nanoparticles.     

Deactivation of Pd particles supported on Nb2O5/Cu3Au(1 0 0): SFG and TPD studies from UHV to 100 mbar

Structural changes that occur on Pd-Nb₂O₅/Cu₃Au(1 0 0) model catalysts upon thermal annealing were followed by sum frequency generation (SFG) and temperature-programmed desorption (TPD) using CO as probe molecule. SFG experiments were performed both under ultrahigh vacuum and mbar pressure. Heating the catalyst to temperatures above 300 K lead to an irreversible 50% decrease in the CO adsorption capacity and modified the remaining adsorption sites. Alterations of the phase between resonant and non-resonant SFG signals upon annealing indicate a change in the electronic structure of the surface, which excludes Pd sintering or migration of Nb₂O₅ over Pd particles to cause the observed effect and rather suggests the formation of “mixed Pd-NbO_x” sites. The same changes in surface properties also occur during CO hydrogenation at 1 bar and high temperature, pointing to an involvement of “mixed Pd-NbO_x” sites in catalytic reactions.     

Co on thin Al2O3 films grown on Ni3Al(1 0 0)

The growth of Co on thin Al₂O₃ layers on Ni₃Al(1 0 0) was investigated by Auger electron spectroscopy, high resolution electron energy loss spectroscopy (EELS), and scanning tunneling microscopy. At 300 K, Co grows in three-dimensional clusters on top of the Al₂O₃ layer. A defect structure of the alumina layer plays a crucial role during the early stage of Co growth. After deposition of 10 Å of Co, a complete screening of the dipoles of the Al₂O₃ layer due to the Co film is found in the EELS measurements. Annealing the Co film reveals a process of coalescence of Co clusters and, above 700 K, diffusion of the Co atoms through the oxide film into the substrate takes place.     

N2-broadening coefficients in the ν4 band of CH4 at room temperature

Using a diode laser spectrometer, we have studied with a great accuracy the N₂-broadening coefficients in the ν₄ band of methane. The experiments were performed at room temperature for lines in the P- and R-branches. We have measured 39 lines in the spectral range 1237–1373 cm⁻¹ with J values between 1 and 12. Each line under study was recorded at four different nitrogen pressures, ranging from 20 to 91 mbar. The collisional half-widths were obtained by fitting individually a theoretical profile on the experimental profile of each line at each N₂-pressure. We fitted the usual Voigt profile, but also the Rautian and Galatry lineshape models which take into account the collisional narrowing due to the molecular confinement (Dicke effect). The Rautian and Galatry fits are always better adjusted on the experimental profiles. For some lines, when the overlapping could not be disregarded, a fit of the blended profiles was performed using the same lineshape models. The collisional broadening coefficients obtained with Galatry and Rautian models are nearly equal and always higher than those derived from Voigt profile. Finally, we compare our results with previous determinations realized for several absorption bands.