Two-dimensional mapping of chemical information at atomic resolution

The simultaneous measurement of structural and chemical information at the atomic scale provides fundamental insights into the connection between form and function in materials science and nanotechnology. We demonstrate structural and chemical mapping in Bi(0.5) Sr(0.5) MnO3 using an aberration-corrected scanning transmission electron microscope. Two-dimensional mapping is made possible by an adapted method for fast acquisition of electron energy-loss spectra. The experimental data are supported by simulations, which help to explain the less intuitive features.     

Simulating the oxygen K-edge spectrum from grain boundaries in ceramic oxides using the multiple scattering methodology

In this paper we demonstrate the use of the multiple scattering methodology to interpret oxygen K-edge spectra from both the bulk and grain boundaries in a variety of ceramic oxides. The experimental electron energy loss spectra (EELS) used in this study, were obtained from a dedicated scanning transmission electron microscope (STEM). Using the STEM to obtain the spectra has the advantage that each spectrum can be acquired with atomic spatial resolution. While the energy resolution is limited to approximately 0.8 eV, and the angular integration in the microscope apertures precludes momentum resolved spectroscopy, this unprecedented spatial resolution allows the electronic structure at individual defect sites to be determined. Additionally, as the microscope can also provide an atomic resolution image of the defect, the relationship between the atomic structure of the defect and its local electronic structure can be determined. In practice, this is achieved by using the structure observed in the image to build the real space atomic cluster for multiple scattering simulations. Detailed interpretation of the simulations of oxygen K-edge spectra from bulk MgO, CaO, SrTiO3, TiO2, MnO2, Mn3O4, Mn2O3 and MnO are presented. In addition, the simulations from grain boundaries in TiO2 (undoped) and SrTiO3 (undoped and Mn doped) are discussed in relation to quantifying the changes in the local electronic structure that are a direct consequence of the defect structure. The simulations are used to make interpretations of the structure-property relationships at these grain boundaries.     

X-ray spectra and valence states of cations in nanostructured half-doped $$\hbox {La}_{0.5}\hbox {Ca}_{0.5}\hbox {MnO}_{3}$$ manganite

Soft X-ray absorption (XAS) and emission (XES) spectroscopies were applied to determine valence states of manganese ions in nanostructured powder of half-doped \(\hbox {La}_{0.5}\hbox {Ca}_{0.5}\hbox {MnO}_{3}\) manganite obtained by milling in a ball mill. XAS spectra were measured both in surface-sensitivity total electron-yield and in bulk-sensitivity total fluorescence-yield modes. O K\(_{\upalpha }\) XES and O 1s XAS spectra characterized the occupied and unoccupied partial O 2p densities of states are compared with band-structure calculations made using the TB-LMTO-ASA codes. Experimental Mn 2p, Ca 2p, and La 3\(d\) XAS spectra are compared with results of crystal field atomic multiplet calculations. For the nanostructured system of \(\hbox {La}_{0.5}\hbox {Ca}_{0.5}\hbox {MnO}_{3}\), concentrations of Mn\(^{4+}\) ions are found to be increased with increasing the time of milling.     

Selective XANES spectroscopy from RIXS contour maps

Kβ resonant inelastic X-ray scattering (RIXS) spectra of Mn and Ga compounds are studied to examine different types of selective XANES. RIXS spectra of MnO in Mn Kβ_1,3 region and of GaCl₂ in Ga Kβ₂ region are plotted as contour maps over wide energy ranges in both excitation and emission. Through analyses of RIXS contour maps by the use of the Kramers-Heisenberg equation, spin-selective XANES spectra are deduced for MnO. In the case of a mixed valence compound GaCl₂ selective XANES of Ga³⁺ ion can be obtained by making use of a large difference in transition probabilities.     

Fine structures in the X-ray photoemission spectra of MnO,FeO, CoO,and NiO single crystals

The main achievements in the study of X-ray photoemission of MnO, FeO, CoO, and NiO, single crystals are discussed. For these compounds the oxygen 1s, the cation 2s, 2p, and 3s core line spectra and the one-electron removal valence band spectra are reported. The unresolved problems in the understanding of the fine structure present in the X-ray photoemission spectra are evidenced.     

Localized electron states and magnetic properties at the interface of a two-dimensional graphene/MnO(001) system

The results of a density functional theory study of the band structure of two-dimensional (2D) graphene/MnO(001), new materials for spintronics, with an antiferromagnetic type of ordering are presented. The regularities of the change of the valence band electron structure in the 3D MnO → 2D MnO → 2D graphene/MnO(001) series have been studied in a comparison with X-ray photoelectron spectra. The stability of the system has been established, and the energy of chemical binding has been determined using the calculation of the structural energy of 2D graphene/MnO(001). The features of the spin state in the valence band—in particular, at the Fermi level—as well as interatomic interaction in 2D graphene/MnO(001) have been discussed in comparison with 2D and 3D MnO systems with antiferromagnetic ordering. The magnetic moment of the Mn atom in all considered systems has been estimated and compared with the experimental one. The effect of the spin polarization for the oxygen and carbon atoms has been detected. The nature of this effect has been considered.     

Nuclear effects in atomic transitions

Atomic electrons are sensitive to the properties of the nucleus they are bound to, such as nuclear mass, charge distribution, spin, magnetisation distribution, or even excited level scheme. These nuclear parameters are reflected in the atomic transition energies. A very precise determination of atomic spectra may thus reveal information about the nucleus, otherwise hardly accessible via nuclear physics experiments. This work reviews theoretical and experimental aspects of the nuclear effects that can be identified in atomic structure data. An introduction to the theory of isotope shifts and hyperfine splitting of atomic spectra is given, together with an overview of the typical experimental techniques used in high-precision atomic spectroscopy. More exotic effects at the borderline between atomic and nuclear physics, such as parity violation in atomic transitions due to the weak interaction, or nuclear polarisation and nuclear excitation by electron capture, are also addressed.     

Colossal magnetoresistance without phase separation: disorder-induced spin glass state and nanometer scale orbital-charge correlation in half doped manganites

The magnetic and electrical properties of high-quality single crystals of A-site disordered (solid solution) Ln0.5Ba0.5MnO3 are investigated near the phase boundary between the spin-glass insulator and colossal-magnetoresistive ferromagnetic metal, locating near Ln=Sm. The temperature dependence of the ac susceptibility and the x-ray diffuse scattering of Eu0.5Ba0.5MnO3 are analyzed in detail. The uniformity of the random potential perturbation in Ln0.5Ba0.5MnO3 crystals with a small bandwidth yields, rather than the phase separation, an homogeneous short ranged charge or orbital order which gives rise to a nearly atomic spin-glass state. Remarkably, this microscopically disordered "charge-exchange-glass" state alone is able to bring forth the colossal magnetoresistance.     

Mn5(PO3(OH))2(PO4)2(H2O)4的水热合成和光谱研究

在水热反应条件下合成出具有红磷锰矿结构的Mn5(PO3(OH) ) 2 (PO4 ) 2 (H2 O) 4单晶 ,在X ray单晶结构分析的基础上 ,对其固体紫外可见漫反射光谱、红外光谱、荧光光谱和热重光谱进行了研究。结果表明 ,构成该化合物的PO4 四面体及MnO6 八面体通过共顶点或共棱方式相连接 ,与P ,Mn配位的氧分为 3类 :即端基氧 (Od)、二桥氧 (Ob)和三桥氧 (Oc)。因而在 2 10和 2 5 0nm左右出现了Od→Mn和Ob ,c→Mn的荷移跃迁吸收谱带 ;在 10 0 0～ 110 0cm- 1 处 ,P—O的伸缩振动峰分裂为 3个 ;70 0～ 980cm- 1 处存在 3类Mn—O的伸缩振动。对标题化合物分别采用 2 18和 310nm的光激发 ,分别在 35 4和 4 13nm产生强而尖锐的荧光光谱发射峰 ,表现了很强的光学效应。热重分析表明该化合物在 2 70℃以下结构保持稳定 ,在 2 70～36 0℃范围内失去配位水。量化计算得单点能为 - 4 5 5 8 6 5 95 5 5 1a u ;前线轨道能量HOMO(Alpha) =- 0 2 80 80a u ,LOMO(Alpha) =0 0 15 2 7a u ,能隙为 0 2 96 0 7a u ;HOMO(Beta) =- 0 2 5 919a u ,LOMO(Beta)=0 0 0 10 8a u ,能隙为 0 2 6 0 72a u ;偶极矩为 4 2 0 82Debye。     

First-principles study of CoO films on MnO (1 1 1): Stability and interfacial structure

Based on the generalized gradient approximation, full potential linearized augmented plane-wave (FP-LAPW) calculations have been performed to study the stability and the interfacial structure of CoO/MnO (1 1 1). The surface energy, the strain energy and the binding energy are calculated and discussed. The calculations revealed that the CoO/MnO (1 1 1) is a stable interface structure. Also examined were the electronic properties and the atomic spin magnetic moments of the interface. It was found that the interface exhibited half-metallic property and the atomic magnetic moments were obviously weakened at the interface for metal atoms compared with the corresponding magnetic moments in bulk material.     

Mechanical damping by intercrystalline diffusion of hydrogen in metallic polycrystals

Anelastic relaxation by intercrystalline atomic diffusion-analogous to thermal diffusion (i.e., thermoelastic) effects but never observed hitherto-was recently suggested as a new mechanism to explain part of the hydrogen damping spectra in intermetallic compounds. A critical experimental test of this model is now presented using a Zr65Cu17.5Ni10Al7.5 alloy, which allows for a quantitative kinetic analysis in comparison to a closely related reorientation process. The results are in full agreement with the predictions of the model and clearly corroborate the proposed "intercrystalline Gorsky effect" as a new type of mechanical damping in sufficiently fine-grained polycrystals.     

Interplay of intra-atomic and interatomic effects: an investigation of the 2p core level spectra of atomic Fe and molecular FeCl2

The 2p photoabsorption and photoelectron spectra of atomic Fe and molecular FeCl2 were studied by photoion and photoelectron spectroscopy using monochromatized synchrotron radiation and atomic or molecular beam technique. The atomic spectra were analyzed with configuration interaction calculations yielding excellent agreement between experiment and theory. For the analysis of the molecular photoelectron spectrum which shows pronounced interatomic effects, a charge transfer model was used, introducing an additional 3d(7) configuration. The resulting good agreement between the experimental and theoretical spectrum and the remarkable similarity of the molecular with the corresponding spectrum in the solid phase opens a way to a better understanding of the interplay of the interatomic and intra-atomic interactions in the 2p core level spectra of the 3d metal compounds.     

紫外激光烧蚀Cu产生等离子体辐射特性

通过时间分辨的光谱测量技术,测定了308 nm XeCl紫外激光烧蚀金属Cu在氮气环境中诱导产生等离子体的发射光谱及其强度随时间分布,实验结果表明等离子体辐射光谱线主要由原子光谱线、一价离子光谱线及连续辐射背景光组成,各种光谱线的数目、辐射强度、持续时间不同。结合实验结果对等离子辐射机理进行了探讨,认为电子通过逆韧致辐射获得较高的能量,连续辐射主要来自高能电子的韧致辐射,原子和一价离子的激发主要是通过电子与原子、离子的碰撞传能以及电子与离子的复合产生,并用其定性地解释了所观察的实验现象。     

Tuning magnetism of MnO by doping with 2p elements

We show that the antiferromagnetic coupling between Mn atoms in MnO can be tuned to a ferromagnetic one by doping it with a small concentration of 2p elements like boron, carbon and nitrogen. Our ab initio density functional calculations in the Hubbard U framework show that the coupling between Mn atoms turns ferromagnetic for 3 at% B doping. B is found to be the most effective one in stabilizing ferromagnetism. We discuss the role of 2p states of the dopant atoms to explain the trend of ferromagnetism in MnO.     

洛阳北魏大市遗址出土玻璃珠成分分析

采用原子吸收光谱法（ＡＡＳ）洛阳北魏大市遗址出土的玻璃珠成分和用Ｘ射线衍射（ＸＲＤ）技术研究了其晶体结构,实验结果显示了玻璃珠主要成分Ｎａ２Ｏ、Ｋ２Ｏ、ＣａＯ、ＭｇＯ、Ｆｅ２Ｏ３、ＣｕＯ、ＰｂＯ、ＭｎＯ、Ａｌ２Ｏ３、ＺｎＯ、ＮｉＯ、ＳｉＯ２和给出了其ＸＲＤ图,并以这些实验数据为依据讨论了玻璃珠的来源及形态。     

硫化锰电子结构的软X射线共振非弹性散射研究

利用软X射线共振非弹性散射谱(resonant inelastic soft X-ray scattering, RIXS)对3d过渡金属硫化物中的硫化锰(MnS)电子结构进行了研究.通过分析Mn²⁺的2p⁶3d⁵→2p⁵3d⁶→2p⁶3d⁵二次光子过程，得到了共振非弹性散射谱中的两类非弹性峰，d-d电子跃迁和电荷转移(charge-transfer)跃迁.这两部分跃迁分别共振增强于L边附近及伴随峰附近.基于Hartree-Fock方法的多重态计算分别模拟了原子近似下和立方体O_h对称群下共振非弹性散射谱及吸收谱.计算得MnS实际晶体场10Dq值介于0.80eV—0.85eV之间.对MnS和MnO CT跃迁差异的讨论表明MnS较强的CT跃迁来源于其较窄的能隙宽度. 关键词： 软X射线共振非弹性散射 软X射线吸收谱 d-d跃迁 电荷转移     

Rescattering for extended atomic systems

Laser-driven rescattering of electrons is the basis of many strong-field phenomena in atoms and molecules. Here, we will show how this mechanism operates in extended atomic systems, giving rise to effective energy absorption. Rescattering from extended systems can also lead to energy loss, which in its extreme form results in nonlinear light-induced trapping. Intense-laser interaction with atomic clusters is discussed as an example. We explain fast electron emission, seen in experimental and numerically obtained spectra, by rescattering of electrons at the highly charged cluster.     

Atomic effects in XUV spectra of solids

The extreme ultraviolet photoabsorption spectra of solids are sometimes dominated by purely atomic effects which manifest themselves in both the fine structure close to and in the gross structure well above thresholds for inner shell excitation. The variation of the relative intensities of structures in photoemission spectra as a function of photon energy can also be attributed to atomic-like effects. Recent experimental results of solid spectra reflecting this behaviour are presented; almost all were obtained using the attractive properties of synchrotron radiation.     

Direct magneto-optical observation of a structural phase transition in thin films of manganites

The spontaneous formation of twins in La(2/3)Ca(1/3)MnO3 films below T(S) approximately 105 K is observed by a magneto-optical technique. The twins are revealed as stripes along the {110} directions where magnetization tilts out of the film plane due to the stresses in twins. Their appearance is associated with a martensitic phase transition in the film triggered by the cubic-to-tetragonal transition in the SrTiO3 substrate. It is found that magnetization of the films proceeds by inhomogeneous rotation of magnetic moments. This is due to the presence of microscopic structural inhomogeneities. Their dominating role in the low-temperature transport can explain small effects of the transition at T(S) on the resistivity.     

Electro-transmission spectra of Li doped NiO and MnO in the visible and near infrared — A new optical effect in 3d semiconductors

Electro-modulation transmission (ET) spectra have been observed in Li doped crystals of NiO and MnO at phonon energies ∼ 0.4–2.5 eV and T < 230 °K. In each case we observe a broad temperature- sensitive peak, centred at 0.9 and 2.1 eV respectively, which we associate with charge carriers bound to Li centres. Modulation probably occurs through a small-polaron mechanism in NiO, and field- enhanced emission in MnO, but the exact mechanism is uncertain. Similar ET spectra have been observed in a doped ferrite.