Study of the electronic structure and properties of 13C-isotope-based composites

The morphology and electronic structure of ¹³C-isotope-based graphite composites were studied by transmission electron microscopy (TEM), x-ray diffraction, and x-ray fluorescence spectroscopy. High-resolution TEM images showed that composites contain several forms of carbon particles. According to an x-ray diffraction analysis, the size of graphene stacks of graphite particles is 20 and 40 Å. The CK _α x-ray fluorescence spectra of the initial ¹³C isotope powder and composites based on it detected an increase in the density of high-energy occupied states in comparison with the graphite spectrum. Ab initio quantum chemical calculation of the structure of C₁₅₀ graphene showed that the increase in the density of states stems from the electrons of dangling bonds of boundary carbon atoms of particles ～20 Å in size. Electrical properties of ¹³C-isotope-based samples were studied by analyzing the temperature dependence of the conductivity. It was assumed that the change in the logarithmic dependence of the conductivity observed at liquid-helium temperatures to the linear dependence as the temperature increases is caused by carrier transfers between the disordered graphene layers forming a nanocomposite.     

X-ray excitons in lithium

A detailed theoretical analysis is made of the x-ray level in metallic lithium with the object of understanding the effect of the electron-hole attraction on the soft x-ray emission spectrum. We regard the conduction electrons as independently scattering off the screened Coulomb field of the inner hole. We find that the resulting distortion of the Bloch functions increases the theoretical emission intensity severalfold. A qualitative general argument and an estimate of the lowest Born approximation to the scattering suggest that the emission spectrum is changed to show a falling intensity at the Fermi level, as is seen experimentally.     

Effect of pressure on the Yb valency in YbS and YbTe

Abstract

We have measured L_III-edge x-ray absorption spectra (L_III-XA) of Yb in YbS and YbTe and optical reflectivity spectra of YbTe at pressures up to 34 GPa. In both materials the Yb ion undergoes a continuous valence change. In the case of YbS, the pressure-induced variation of the Yb mean valence v(I_III) agrees well with previous optical and lattice parameter studies. For YbTe, however, the XA data indicate the onset of a valence transition at a lower pressure (～10 GPa) than observed in optical spectra (～16 GPa). This behavior is explained by larger hybridization effects between the chalcogen p-bands and 4f states in YbTe as compared to YbS.     

X射线吸收近边结构理论

在X射线吸收谱中,阈值之上60eV以内的低能区的谱出现强的吸收特性,称之为近边吸收结构(XANES)。它是由于激发光电子经受周围原子的多重散射造成的。它不仅反映吸收原子周围环境中原子几何配置,而且反映凝聚态物质费米能级附近低能位的电子态的结构。因此成为研究凝聚态物质的有用工具。本文较详细地介绍了XANES理论中的多重散射模型与计算方法。同时,也揭示多重散射理论与广延系统中通常采用的能带结构理论以及有限系统中的单电子的分子轨道方法之间的关系。并给出若干实例以说明XANES的多重散射理论的应用。     

Bonding of saturated hydrocarbons to metal surfaces

The adsorption of octane on Cu(110) was studied by x-ray absorption and x-ray emission spectroscopy, in combination with spectrum calculations in the framework of density functional theory, as a model system for alkane adsorption on transition metals. Significant electron sharing between the adsorbate and metal surface and involvement of both bonding and antibonding C-H molecular orbitals in the molecule-metal bond was found. The calculations were extended to the case of octane adsorbed on Ni(110), and the position of the metal d band was found to be important for the bonding. The results were generalized to show that this is important for the efficiency as an alkane dehydrogenation catalyst.     

Determination of diffusion profiles in thin film couples by means of x-ray-diffraction

An x-ray method for the determination of concentration profiles in thin film diffusion couples is presented. This method is based on the theory of Fourier analysis of x-ray diffraction profiles which is generalized to polycrystalline samples showing nonuniform lattice parameter. A Fourier synthesis of the concentration spectrum is possible when the influences of the particle size and the strain in the sample as well as the instrumental function are eliminated from the measured diffraction profile. This can be done by means of reference profiles obtained from layers of the diffusion components. Absorption of the radiation in the sample is negligible when diffusion couples of symmetrical sandwich structure are used. The method is tested experimentally in the system Au-Cu.     

Near-edge x-ray absorption fine-structure investigation of graphene

We report the near-edge x-ray absorption fine-structure (NEXAFS) spectrum of a single layer of graphite (graphene) obtained by micromechanical cleavage of highly ordered pyrolytic graphite on a SiO2 substrate. We utilized a photoemission electron microscope to separately study single-, double-, and few-layers graphene samples. In single-layer graphene we observe a splitting of the pi resonance and a clear signature of the predicted interlayer state. The NEXAFS data illustrate the rapid evolution of the electronic structure with the increased number of layers.     

氢掺杂单层石墨体系的晶格动力学研究

采用密度泛函理论研究了氢掺杂单层石墨（graphene）体系,并采用密度泛函微扰理论方法计算了体系局域振动模（LVMs）.结果显示,高频位置的LVMs数目与缺陷中氢原子数相等,而不同掺杂类型的LVMs频谱位置各不相同.研究结果及分析表明,LVMs测量是评估质子辐射下石墨样品的替位氢掺杂类型及其含量的有效方法,该方法可推广应用于研究其他掺杂体系. 关键词： 石墨 局域模式 晶格动力学     

Gas-phase synthesis of nitrogen-containing carbon nanotubes and their electronic properties

Nitrogen-containing carbon nanotubes are synthesized using a gas-phase reaction. The synthesis of nitrogen-doped carbon nanotubes from 100 to 500 Å in diameter is accomplished through pyrolysis of acetonitrile (CH₃CN) at a temperature of 800°C. Cobalt and nickel metallic particles formed upon thermal decomposition of a mixture of maleate salts are used as catalysts. The materials synthesized are investigated by scanning and transmission electron microscopy. Analysis of the x-ray photoelectron spectra demonstrates that the content of nitrogen atoms in three nonequivalent charge states is approximately equal to 3%. A comparison of the CK _α x-ray fluorescence spectrum of the carbon nanotubes synthesized through electric-arc evaporation of graphite and the x-ray fluorescence spectrum of the nitrogen-containing carbon nanotubes prepared by catalytic decomposition of acetonitrile indicates that, in the latter case, the spectrum contains a certain contribution from the sp ³ states of carbon atoms. The temperature dependences of the electrical conductivity for different types of multi-walled carbon nanotubes are compared. The difference observed in the temperature dependences of the electrical conductivity is associated with the presence of additional scattering centers in nitrogen-containing carbon nanotubes.     

Phase analysis of quantum oscillations in graphite

The quantum de Haas-van Alphen (dHvA) and Shubnikov-de Haas oscillations measured in graphite were decomposed by pass-band filtering onto contributions from three different groups of carriers. Generalizing the theory of dHvA oscillations for 2D carriers with an arbitrary spectrum and by detecting the oscillation frequencies using a method of two-dimensional phase-frequency analysis which we developed, we identified these carriers as (i) minority holes having a 2D parabolic massive spectrum p(2)(perpendicular)/2m(perpendicular), (ii) massive majority electrons with a 3D spectrum and (iii) majority holes with a 2D Dirac-like spectrum +/-vp(perpendicular) which seems to be responsible for the unusual strongly-correlated electronic phenomena in graphite.     

紫外激发下锰掺杂纳米氧化锌

应用气相传输法, 以铜为催化剂, 在硅衬底上制备了锰掺杂氧化锌纳米四足晶须. 利用x射线与电子衍射谱、扫瞄电镜和高分辨率透射电镜, 对样品形貌、结构和成份进行表征与检测; 通过355nm与375nm紫外光激发下掺杂与未掺杂样品光致发光谱的对比, 结合拉曼散射谱与光致激发谱对掺杂样品中反常光致发光机理进行分析. 结果表明, 样品沿［0001］方向生长的前端和内部长有纤细刺状结构的中空六方管组成; 样品中掺入Mn2+的无辐射复合中心作用, 是掺杂样品紫外辐射强度和谱宽变小的主要原因, 氧化锌晶体中晶格周期对Mn2+中d-d电子跃迁过程的影响, 是375nm紫外光激发下掺杂样品中415nm辐射峰产生的主要原因.     

快速电子验证相对论效应实验中几个问题的分析

快速电子验证相对论实验是近代物理实验中一个极其重要的实验，本对实验得到的能谱曲线中的两个峰作了详细分析，并证明该实验不仅可以用来验证相对论，也可以用来验证全同粒子的不可分辨性以及X射线特征谱线与入射电子能量无关，只与靶材料有关的理论。     

Crystal structure of cold compressed graphite

Through a systematic structural search we found an allotrope of carbon with Cmmm symmetry which we predict to be more stable than graphite for pressures above 10 GPa. This material, which we refer to as Z-carbon, is formed by pure sp(3) bonds and it provides an explanation to several features in experimental x-ray diffraction and Raman spectra of graphite under pressure. The transition from graphite to Z-carbon can occur through simple sliding and buckling of graphene sheets. Our calculations predict that Z-carbon is a transparent wide band-gap semiconductor with a hardness comparable to diamond.     

Effective screening of hydrodynamic interactions in charged colloidal suspensions

We investigate the hydrodynamic interaction in suspensions of charged colloidal silica spheres. The volume fraction as well as the range of the electrostatic repulsion between the spheres is varied. Using a combination of dynamic x-ray scattering, cross-correlated dynamic light scattering, and small angle x-ray scattering, the hydrodynamic function H(q) is determined experimentally. The effective hydrodynamic interactions are found to be screened, if the range of the direct interaction is relatively long and the static density correlations are strong. This observation of effective hydrodynamic screening is in marked contrast to hard-sphere-like systems.     

Theoretical calculations of the energies of the ∝ satellite and hypersatellite lines of magnesium

The satellite and hypersatellite x-ray lines which lie on the high energy side of the dipole ∝_1,2 lines are generally attributed to multiple ionization. In this paper, an attempt is made to calculate the energies of these lines in the x-ray spectrum of the magnesium atom using screened hydrogenic wavefunctions. Besides the good agreement found between our calculated values and the experimental results, our calculations give some additional lines not reported earlier.     

Auger and emission spectra of carbon nanotubes

The Auger and x-ray emission spectra of carbon nanotubes are calculated by the FP-LMTO method. The computed spectra for nanotubes are compared to the analogous spectra for a graphite monolayer, which is used as a test object, and to the experimental curves for graphite. It is concluded that the Auger-characteristic emission can be used to identify carbon nanotubes. Fiz. Tverd. Tela (St. Petersburg) 41, 1511–1514 (August 1999)     

Physisorption-induced C-H bond elongation in methane

Physisorption of methane to a Pt surface was studied by x-ray absorption spectroscopy in combination with density functional theory spectrum calculations. The experiment shows new electronic states appearing upon physisorption. We find that these states are due to orbital mixing causing charge polarization as a means to minimize Pauli repulsion. The results can be explained by elongation of 1 C-H bond by 0.09 A in the physisorbed state even though no covalent chemical bond is formed.     

Core-level x-ray photoemission satellites in ruthenates: a new mechanism revealing the Mott transition

Core-level x-ray photoemission spectra for the Mott-Hubbard systems are calculated by the dynamical mean-field theory based on the exact diagonalization method. The spectra show a two-peak structure, screened and unscreened peaks. The screened peak is absent in a Mott insulator, but develops into the main peak when the correlation strength becomes weak and the system turns metallic. The calculated spectral behavior is consistent with the experimental Ru 3d core-level spectra of various ruthenates. This new mechanism of the core-level photoemission satellite can be utilized to reveal the Mott transition phenomenon in various strongly correlated electron systems, especially in nanoscale devices and phase-separated materials.     

Comparison of the CKLL first-derivative auger spectra from XPS and AES using diamond,graphite, SiC and diamond-like-carbon films

The carbon KLL first-derivative Auger spectra obtained by numerically differentiating the XPS N(E) line gives a better fine-structure fingerprint of the carbon state than conventional AES. The first-derivative of the X-ray excited (XAES) CKLL spectrum from a diamond-like-carbon (DLC) film exhibited almost the same spectrum as both the XAES and AES spectra from natural diamond. However, the AES spectrum of the DLC film indicated a graphite-like structure due to electron beam damage. Comparison of the XAES and AES spectra suggested that the electron beam used in conventional AES partially changed the plasmon loss structure of carbon in diamond, graphite and β-SiC as well.     

Polarization propagator for x-ray spectra

A polarization propagator for x-ray spectra is outlined and implemented in density functional theory. It rests on a formulation of a resonant-convergent first-order polarization propagator approach which makes it possible to directly calculate the x-ray absorption cross section at a particular frequency without explicitly addressing the excited states. The quality of the predicted x-ray spectrum relates only to the type of density functional applied without any separate treatment of dynamical relaxation effects.