Stabilization of valence fluctuations in the cerium solid by the time-dependent collision approach

The collision-generated hybridization which has been found responsible for the on-site mixing of the atomic-likef-state and the band-liked states in mixed valence solids has been studied for the cerium solid. A practical expression which depends on the lattice constant and temperature has been obtained for the collision-generated hybridization. Numerical calculations show that the valence varies continuously with lattice constant and that temperature makes the transition smoother. The collision-generated hybridization is found to be of significant strength in the intermediate valence regime; but over a wide range of the valence near 3.5 it varies rather slowly without preferring a particular valence. Factors which can assist the collision-generated hybridization in stabilizing the mixed valence phase at a particular lattice constant are discussed.     

An exact limit of a local mixed valence model

Recently, Khomskii and Kocharjan have considered a local mixed valence model and, in a generalized linear Hartree-Fock approximation, found solutions which, when generalized to the many site problem, displayed continuous and discontinuous transitions from ground states of integral to intermediate valence. The transitions were due to an energy dependence of the virtual bound state width and persisted in the limit of zero hybridization. We examine the model of Khomskii and Kocharjan and demonstrate that in the limit of zero hybridization an exact solution may be found for the valence behaviour. The generalization of this result to the case of a small but finite concentration of localized level sites, exhibits intermediate valence only as a consequence of the pinning of the Fermi level to the narrow localized levels and the transitions between the ground states of integral and intermediate valence are continuous.     

The XPS valence band of nickel metal

The XPS valence band spectrum of evaporated nickel is compared with a theoretical density of states curve and with a synthetic density of states curve obtained by adding two XPS valence band spectra of copper shifted by 0.3eV with respect to each other. Both calculated curves agree with the main features of the XPS valence band spectrum.     

Valence state mapping of cobalt and manganese using near-edge fine structures

The properties of transition metal oxides are related to the presence of elements with mixed valences. The spectroscopy analysis of the valence states is feasible experimentally, but a spatial mapping of valence states of transition metal elements is a challenge to existing microscopy techniques. In this paper, with the use of valence state information provided by the white lines and near-edge fine structures observed using the electron energy-loss spectroscopy (EELS) in a transmission electron microscope (TEM), a novel experimental approach is demonstrated to map the valence state distributions of Mn and Co using the ratio of white lines in the energy-filtered TEM. The valence state map is almost independent of specimen thickness in the thickness range adequate for quantitative EELS microanalysis. An optimum spatial resolution of approximately 2 nm has been achieved for a two-phase Co oxides.     

Valence variations of Sm on polycrystalline Ag

Thin deposited films of Sm on a polycrystalline Ag are investigated by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and photoemission electron microscopy (PEEM). The Sm valence is mainly divalent for low Sm coverage, while the trivalent contribution to the XPS intensity increases considerably for higher coverage. For an Sm overlayer thicker than 4 Å, the average valence is estimated to be 2.65. The mixed valence in this system is concluded to be heterogeneous (all Sm atoms have integer and site-dependent valence). Alloy formation between Sm and Ag is observed upon annealing to temperatures between 400 and 550 °C. For these temperatures the change in average Sm valence is dependent on the initial Sm coverage deposited onto the Ag-foil. Systems with low initial coverage exhibit an increase in the average valence, while a decrease is observed for systems with coverage above 6 Å. For intermediate coverages around 3 Å an initial decrease in average valence is followed by a rapid increase for temperatures above 400 °C due to morphological changes in the surface layer.     

价键优选法及其在纳米结构预测与物性研究中的应用

本文论述价键优选法作为一种新颖的理论方法在材料结构预测与物性研究中的应用, 特别是在低维数纳米结构如团簇与纳米线研究中所展示的优势. 价键优选法以原子几何构型和电子云(主要是由费米能级附近的分子轨道组成, 即广义前线轨道)空间分布来合理决定纳米结构的稳定构型的选取. 本文以硅团簇为例说明价键优选法的特点, 以及锂、钠、铍、镁等金属团簇为例说明价键优选法在结构预测与材料 物性随尺寸演化规律研究中的应用, 以锂离子在MoS纳米线中的吸附为例说明价键优选法在储能材料离子传导研究中的应用, 最后总结价键优选法的进一步发展方向. 关键词： 价键优选法 团簇 纳米结构 离子传导     

Pressure induced configuration demixing in the electronic spectrum of NO

Previous low resolution studies indicated that, in the absorption spectrum, transitions to Rydberg states are far more sensitive to pressure than transitions to valence states in accordance with the complete vanishing of Rydberg bands and the deperturbation of the valence bands in the spectrum of NO trapped in a solid rare gas matrix. The present study of NO is the first extensive investigation of medium and high resolution molecular electronic spectra subjected to pressure of foreign gases. It is observed that, at the highest pressure attained (～1000 bar), almost all of the Rydberg bands have vanished whereas the remaining valence bands stay relatively sharp. While high pressure medium resolution spectra give information about the deperturbation of intensities and of vibrational spacings of the valence bands, inspection of low pressure high resolution spectra reveals that the rotational lines react to pressure in a way reflecting closely the degree of configuration mixing between Rydberg and valence states.     

Stabilization of mixed valence by polaronic effects

Polaronic effects in mixed valence systems are studied in a simple model of localized d-electrons for arbitrary values of relevant parameters. Variational approach is used which permits one to interpolate between the limit of average static lattice distortion and that of different local distortions for different valence states of an ion. It is shown that the degree of local electron-lattice correlation and polaron narrowing of virtual f-level changes with a position of f-level. Polaronic effects make a valence transition more gradual and stabilize mixed valence phase. At the end some comments on a possibility of Valence Density Waves in mixed valence compounds are made and certain properties of CeAl₂ are tentatively ascribed to them.     

Synthesis mechanism of nanoporous Sn_3O_4 nanosheets by hydrothermal process without any additives

Nanoporous anorthic-phase Sn3O4 nanosheets are successfully fabricated via a hydrothermal process without any additives.With the p H value of the precursor increasing from 2.0 to 11.8,the valence of the precursor changes from mixed valence(the ratio of Sn2+to Sn4+is 2.7:1) to pure bivalent,and the product transformed from Sn3O4 to Sn O mesocrystals.When doping Sb Cl3 to the alkaline precursor,the valence of the precursor shows mixed valence with the ratio of Sn2+to Sn4+being 2.6:1 and Sn3O4 is synthesized after the hydrothermal process.The valence state of Sn species in the precursor is the key factor of the formation of Sn3O4.The synthesis mechanism is discussed and proposed.These experimental results expand the knowledge base that can be used to guide technological applications of intermediate tin oxide materials.     

焙烧条件对Ce离子价态影响的XPS研究

在均相沉淀法制备含铈化合物的过程中,利用XRD和IR尤其是XPS研究了含Ce化合物在不同焙烧温度条件下产物的结构、铈离子的价态变化、化合物表面性质及其内核电子构型。XRD结果表明,焙烧温度的不同可产生不同的铈基化合物,导致产物中Ce离子价态的变化,IR结果也证实了这一点。单纯均相沉淀法得到的产物为三价的斜方晶系的单晶Ce_2O(CO_3)_2·H_2O(Ⅲ)微粒;将三价的Ce_2O(CO_3)_2·H_2O加热到200℃,产物转化成高价态六价化合物CeO(CO_3)_2·H_2O(Ⅵ);加热温度再升高到250℃,产物转化为稳定的四价化合物CeO_2(Ⅳ)。XPS通过对3种不同价态化合物的O(1s),Ce(3d),Ce(4d)峰进行精细扫描,研究了产物的表面性质及其内部电子构型,比较结果证实了不同价态铈化合物的形成是由于内核价电子构型的差异引起的。     

Pressure-induced valence crossover in superconducting CeCu2Si2

Measurement of the Ce valence in the heavy fermion CeCu(2)Si(2) is reported for the first time under pressure and at low temperature (T=14 K) in proximity of the superconducting region. CeCu(2)Si(2) is considered as a strong candidate for a new type of pairing mechanism related to critical valence fluctuations which could set in at high pressure in the vicinity of the second superconducting dome. A quantitative estimate of the valence in this pressure region was achieved from the measurements of the Ce L(3) edge in the high-resolution partial-fluorescence yield mode and subsequent analysis of the spectra within the Anderson impurity model. While a clear increase of the Ce valence is found, the weak electron transfer and the continuous valence change under pressure suggests a crossover regime with the hypothetical valence line terminating at a critical end point T(cr) close to zero.     

Valence band x-ray emission spectra of compressed germanium

We report measurements of the valence band width in compressed Ge determined from x-ray emission spectra below the Ge K edge. The width of the valence band does not show any pressure dependence in the semiconducting diamond-type structure of Ge below 10 GPa. On the other hand, in the metallic beta-Sn phase above 10 GPa the valence band width increases under compression. Density-functional calculations show an increasing valence band width under compression both in the semiconducting phase (contrary to experiment) and in the metallic beta-Sn phase of Ge (in agreement with observed pressure-induced broadening). The pressure-independent valence band width in the semiconducting phase of Ge appears to require theoretical advances beyond the density-functional theory or the GW approximation.     

Contribution of valence s+p type electrons to the high momentum components of the electron-positron momentum density in gold

It is generally believed that the high momentum components (HMCs) of the angular correlation of annihilation radiation or Doppler broadening spectra map the positron annihilation with predominately core electrons, containing only a small fraction coming from localised d+f-type valence electrons. In present work, we study how far the contribution of valence electrons to the HMCs of the electron-positron (e-p) momentum density can be neglected. Calculations are performed for gold within both the independent particles model (IPM) and including the e-p correlation effects non-locally, using the weighted density approximation (WDA). In particular, the HMCs due to valence s+p-type electrons are compared with their core and d+f-type valence counterparts.     

Electrical resistivity of Sm monochalcogenides

The resistivity of mixed valence compounds has been computed in a two band Hubbard-like model. It is shown that there is a transition from a semiconductor to a metallic conductivity and that an intermediate valence can be found in both phases.     

平均价电子数与掺杂铁基砷化物超导电性关系

文中提出一个计算掺杂铁基砷化物平均价电子数的方法,研究了掺杂铁基砷化物平均价电子数Zv 和转变温度Tc之间的关系,发现他们之间有一定的规律性,由此,提出用平均价电子数作为提高掺杂铁基砷化物超导电性的一个新依据.     

Electron-nucleon resonance model of valence bond

The formation of valence bonds is traditionally considered as the displacement of electronic orbitals in space between interacting atoms. At the same time, a number of experimental facts, in particular, the existence of four-dimensional structural symmetry between the filling of electron shells and periodic properties of elements, require a change in the standard valence concept. A model in which valence bonds are caused by the resonant interaction between the shell electrons of one atom and the protons of another atom seems to be more adequate. The text was submitted by the authors in English.     

Synchrotron radiation study of the photoionization cross sections for the whole valence band of 2H-MoS2

The first complete analysis of photoionization cross section in the whole valence band of 2H-MoS₂ is reported. The measurements, taken with synchrotron radiation in the 65–190 eV energy range, allow the identification of the Mo 4d contribution to the electron states in the different regions of the valence density of states. In particular it is found that the deepest valence peak contains a considerable 4d contribution.     

Electron attachment to strongly polar clusters

Electron localization is studied in formamide cluster anions. The isolated formamide molecule has a large dipole moment and its clusters can give birth to multipole-bound anions as well as valence anions. The vertical valence electron affinity of the isolated molecule is determined by electron transmission spectroscopy. The anion formation process is studied as a function of cluster size with Rydberg electron transfer spectroscopy. DFT calculations of the neutral and negatively-charged cluster structures show that the anion excess electron localizes on a single molecule. The adiabatic valence electron affinity of isolated formamide is deduced from the observation of the cluster size threshold for valence attachment.     

Valence transition and magnetic ordering in Sn doped EuPd2Si2

The sharp, temperature induced, continuous valence transition in EuPd₂Si₂ is drastically changed by doping with Sn at the Si site upto 5 at. %. Only a first order valence transition occurs for a 3% Sn doped sample and the 2⁺ component which survives the valence transition orders magnetically at 4.2 K. No valence transition at all occurs for a 5% Sn doped sample right up to 1.9 K and magnetic ordering sets in around 30 K.