Direct observation of the mass renormalization in SrVO3 by angle resolved photoemission spectroscopy

Band dispersions and Fermi surfaces of the three-dimensional Mott-Hubbard system SrVO3 are directly observed by angle-resolved photoemission spectroscopy. An observed spectral weight distribution near the Fermi level (E(F)) shows cylindrical Fermi surfaces as predicted by band-structure calculations. By comparing the experimental results with calculated surface electronic structures, we conclude that the obtained band dispersion reflects the bulk electronic structure. The enhanced effective electron mass obtained from the energy band near E(F) is consistent with the bulk thermodynamic properties and hence with the normal Fermi-liquid behavior of SrVO3.     

Fermi surface of 3d1 perovskite CaVO3 near the Mott transition

We present a detailed de Haas-van Alphen effect study of the perovskite CaVO3, offering an unprecedented test of electronic structure calculations in a 3d transition metal oxide. Our experimental and calculated Fermi surfaces are in good agreement, but only if we ignore large orthorhombic distortions of the cubic perovskite structure. Subtle discrepancies may shed light on an apparent conflict between the low energy properties of CaVO3, which are those of a simple metal, and high energy probes which reveal strong correlations that place CaVO3 on the verge of a metal-insulator transition.     

A density functional study of plutonium dioxide

The electronic and geometric structures of bulk PuO₂ and its (110) surface have been studied using a periodic model within the generalized gradient approximation (GGA) of density functional theory (DFT). The sixty core electrons of the Pu atom have been represented by a relativistic effective core potential and scalar relativistic effects have been incorporated on the valence orbitals. For bulk PuO₂, we predict an equilibrium lattice constant of 10.10 a.u. and a cohesive energy of 17.28 eV, in good agreement with experimental data. For the (110) surface, upon relaxation, the distance between the top layer and the next layer is found to decrease by 0.12 ?, i.e. 5.3% of the corresponding interlayer distance in the bulk. The distance between the two oxygen atoms on the top layer is found to increase by 0.15 ?, i.e. 5.6% of the corresponding bulk value. The small surface relaxation energy of 0.268 eV per unit cell indicates the fair stability of this surface. The effective charges on Pu and O atoms show that the chemical bonding in this system is not purely ionic. Together with the metallic feature of the density of states (DOS) on the surface, the effective charge distribution provides some basis for understanding surface reactivity and corresponding support for catalysis. Received 16 June 2000     

Ab initio calculations study of the electronic, optical and thermodynamic properties of NaMgH3, for hydrogen storage

The structural stability, electronic structure, optical and thermodynamic properties of NaMgH₃ have been investigated using the density functional theory. Good agreement is obtained for the bulk crystal structure using both the local density approximation (LDA) and the generalized gradient approximation (GGA) for the exchange-correlation energy. It is found from the electronic density of states (DOS) that the valence band is dominated by the hydrogen atoms while the conduction band is dominated by Na and Mg empty states. Also, the DOS reveals that NaMgH₃ is a large gap insulator with direct band gap 3.4 eV. We have investigated the optical response of NaMgH₃ in partial band to band contributions and the theoretical optical spectrum is presented and discussed in this study. Optical response calculation suggests that the imaginary part of dielectric function spectra is assigned to be the interband transition. The formation energy for NaMgH₃ is investigated along different reaction pathways. We compare and discuss our result with the measured and calculated enthalpies of formation found in the literature.     

Adsorption and Reaction of CO on （100） Surface of SrTiO3 by Density Function Theory Calculation

Adsorption and reaction of CO on two possible terminations of SrTiO3 （100） surface are investigated by the first-principles calculation of plane wave ultrasoft pseudopotentiai based on the density function theory. The adsorption energy, Mulliken population analysis, density of states （DOS） and electronic density difference of CO on SrTiO3 （100） surface, which have never been investigated before as far as we know are performed. The calculated results reveal that the Ti-CO orientation is the most stable configuration and the adsorption energy （0.449eV） is quite small. CO molecules adsorb weakly on the SrTiO3 （100） surface, there is predominantly electrostatic attraction between CO and the surface rather than a chemical bonding mechanism.     

用LMTO方法对清洁Nb(100)面电子结构的研究

用LMTO-ASA方法计算了铌的体态密度和清洁Nb(100)表面的局域态密度以及有关的表面能。所计算的体态密度与用其它方法计算的态密度符合得很好,表面能则支持了低能电子衍射(LEED)动力学计算的结果,并且通过分析表面局域态密度,提出了清洁Nb(100)表面存在表面态,表面态位于费密能级的上方。 关键词：     

Electronic properties of TiC(100) and polar TiC(111) surfaces

The energy bands of films of TiC have been calculated using the linear-combination-of-atomic-orbitals method with parameters obtained by a fit to the bulk band structure. The Madelung potentials and charge redistribution have been determined self-consistently. For the neutral TiC(100) surface, the density of states (DOS) is similar to that of the bulk. For the non-neutral Ti-covered TiC(111) surface, Ti 3d-derived surface states appear around the Fermi energy E_F. The long-range electric field produced by the polar surfaces is screened by the charge redistribution, and the polar surfaces are stabilized. Characteristic features of TiC(111) compared to other surfaces of TiC are attributed to the high surface DOS at E_F.     

Band structure,Fermi surface,elastic,thermodynamic,and optical properties of AlZr_3,AlCu_3,and AlCu_2Zr:First-principles study

The electronic properties(Fermi surface,band structure,and density of states(DOS)) of Al-based alloys AlM_3(M=Zr and Cu) and AlCu_2Zr are investigated using the first-principles pseudopotential plane wave method within the generalized gradient approximation(GGA).The structural parameters and elastic constants are evaluated and compared with other available data.Also,the pressure dependences of mechanical properties of the compounds are studied.The temperature dependence of adiabatic bulk modulus,Debye temperature,specific heat,thermal expansion coefficient,entropy,and internal energy are all obtained for the first time through quasi-harmonic Debye model with phononic effects for T = 0 K-100 K.The parameters of optical properties(dielectric functions,refractive index,extinction coefficient,absorption spectrum,conductivity,energy-loss spectrum,and reflectivity) of the compounds are calculated and discussed for the first time.The reflectivities of the materials are quite high in the IR-visible-UV region up to ~ 15 eV,showing that they promise to be good coating materials to avoid solar heating.Some of the properties are also compared with those of the Al-based Ni_3 Al compound.     

立方K2CsSb、K3Sb和Cs3Sb阴极材料的电子结构和光学性质

针对K2CsSb光电阴极生长过程中可能存在的K3Sb、K2CsSb和Cs3Sb三种化合物,采用基于密度泛函理论的第一性原理计算方法,分别建立这三种锑化物阴极材料的立方结构体模型和(111)表面模型,获得了其电子结构与光学性质.对于体模型,计算得到了能带结构、态密度和光学性质,而对于表面模型,计算得到了功函数、光学性质和表面能.结果表明,三种锑化物阴极在中微子与闪烁体作用辐射能量范围(2.4~3.2eV)内,K2CsSb体材料的吸收系数和反射率与Cs3Sb、K3Sb体材料相近,而K2CsSb(111)表面的吸收系数和反射率低于其他两种阴极的(111)表面.此外,K3Sb的禁带宽度最小、功函数最大且表面能最大,Cs3Sb的表面能最小,其功函数与K2CsSb相近但禁带宽度比K2CsSb小,而K2CsSb禁带宽度最大,功函数和表面能都较小,因此K2CsSb阴极在蓝紫光波段适合作为一种稳定高效的光电发射材料.     

Influence of acceptor and donor adsorbates (CO,K, NH3) on Pt surface core-level shifts

4f core-level shifts have been measured for clean surfaces of Pt(111), Pt(331), and Pt(557). Surface peaks due to terrace sites are shifted toward lower binding energy (0.32 ± 0.05 eV) from the bulk peak, whereas peaks from step atoms are shifted by 0.58 ± 0.05 eV also to lower binding energy. The intensity ratios for the two sites differ considerably between the stepped Pt surfaces. Chemisorption of carbon monoxide on the Pt(331) surface is preferential to step sites, with a Pt 4f binding energy shift of ～ 1.29 eV toward higher binding energy. Chemisorption of potassium and ammonia also produces Pt 4f surface shifts which are at higher binding energy than the bulk peak. These experiments do not support the concept of electron donation by these adsorbates into metal d orbitals. The results are discussed in view of, and supported by, tight-binding LCAOMO calculations of potassium and ammonia interacting with a Pt(111) thin film.     

Oxygen diffusion in SrZrO3

Oxygen diffusion coefficients in SrZrO₃ polycrystals were determined using the isotopic exchange method with ¹⁸O as oxygen tracer. Diffusion treatments were performed at different temperatures between 1173 K and 1473 K. Oxygen diffusion profiles were established by secondary ion mass spectroscopy (SIMS). Classical diffusion equations were used to fit experimental results and to determine bulk diffusion (D_vol) and surface exchange (k) coefficients of oxygen in SrZrO₃ polycrystalline materials. From these values, bulk diffusion and grain boundary diffusion coefficients as well as oxygen surface exchange coefficients were determined. The activation energy of oxygen diffusion in the bulk is 2.1 eV, while for the diffusion in the grain boundary, 1.8 eV was found. The surface exchange reaction has an activation enthalpy of 1.2 eV.     

Polar discontinuity doping of the LaVO_{3}/SrTiO_{3} interface

We have investigated the transport properties of LaVO_{3}/SrTiO_{3} Mott-insulator-band-insulator heterointerfaces for various configurations. The (001)-oriented n-type VO_{2}/LaO/TiO_{2} polar discontinuity is conducting, exhibiting a LaVO3 thickness-dependent metal-insulator transition and low temperature anomalous Hall effect. The (001) p-type VO_{2}/SrO/TiO_{2} interface, formed by inserting a single layer of bulk metallic SrVO3 or SrO, drives the interface insulating. The (110) heterointerface is also insulating, indicating interface conduction arising from electronic reconstructions.     

四角晶相HfO2(001)表面原子和电子结构研究

采用基于第一性原理的密度泛函理论研究了四角晶相二氧化铪(t-HfO₂)体相及 其(001)表面的原子几何与电子结构.理论计算结果表明，t-HfO₂(001)表面不会 产生重构现象.与体相电子结构相比, t-HfO₂(001)表面态密度明显高于体相态 密度.其次，表面原子的态密度更靠近费米能级(E_F)，价带往低能量处移动，并 有表面态产生.计算结果表明了t-HfO₂表面禁带宽度明显低于体相的禁带宽度. t-HfO₂(001)的表面态产生以及表面禁带宽度减小是由于Hf原子与O原子的配位 数减少，表面原子周围的环境发生变化而引起的. 关键词： 密度泛函理论 2(001)')" href="#">t-HfO₂(001) 表面电子结构     

单原子Al修饰空位缺陷V2C（MXene）对H2气体表面吸附的第一性原理研究

基于第一性原理计算方法,对含空位缺陷的V₂C(MXene)在不同位点修饰单原子Al的相关性能进行系统研究.研究表明,几何优化后得到含空位缺陷的V₂C稳定结构表面能为-3075.53 J/m²,单原子Al修饰本征V₂C单原子的吸附能为1.5511eV、单原子Al修饰空位缺陷V₂C的吸附能为-2.0763 eV,这表明含空位缺陷的V₂C,由于单原子Al的修饰可以明显改善晶体结构稳定性.进一步从态密度、分波态密度、吸氢能力研究发现,各体系态密度和分波态密度均出现分波越过费米能级的现象,表现出较强的金属性;V₂C吸附H₂气体分子吸附能为-7.5867 eV,而空位缺陷V₂C和单原子Al修饰空位缺陷V₂C两个体系对H₂气体分子的吸附能仅为-0.9851 eV、-2.7130 eV,均未能进一步改善V₂C对H₂气体分...     

A self-modeling approach to the resolution of XPS spectra into surface and bulk components

A method of resolving XPS spectra into surface and bulk component spectra for cases of moderate energy resolution is designed based on an analysis of a family of spectra acquired at different polar angles from flat specimens. Assumptions about line shapes are not required, but an analytical model of the angular dependence of the bulk and surface XPS signals is needed when the component spectra overlap in the range of binding energies of interest. Recommendations are made of the error limits of experimental variables for the successful application of the self-modeling method. The method was used successfully in the separation and quantitative analysis of the O(1s) XPS spectra of surface silanols from bulk silicon dioxide of a fully hydrated silicon dioxide surface. The surface (silanol) and bulk (oxide) components were found to be separated by 0.30 eV, and the surface component was found to be broader (1.58 eV) than the bulk component (1.15 eV).     

Determination of the thickness and density of the ion bombardment induced altered layer in SiC by means of reflection electron energy loss study

The steady state surfaces of ion bombarded 3C-, 4H- and 6H-SiC samples were studied by means of reflected electron energy loss spectroscopy (REELS). The REELS exhibit a well-defined loss peak in the region of about 20 eV. The position of the maximum of the loss peak depends on the bombarding ion energy (decreasing with increasing ion energy), and on the primary electron beam energy (increasing with increasing primary energy). This behavior can be explained if we suppose that the plasmon energy in the altered layer (produced by ion bombardment) is different from that of the unaltered bulk. In this case the measured loss peak is the sum of two overlapping plasmon peaks. With modeling the system as a homogeneous altered layer and a homogeneous unaltered substrate the plasmon energy in the altered layer was derived to be 19.8 eV. The large change of the plasmon energy with respect to the bulk value of 23 eV is explained by a thin low density overlayer on the surface of the sample produced by the ion bombardment.     

Surface gap and surface electronic states in CuGeO3 single crystal

The surface and bulk electronic excitations of CuGeO₃ are investigated by means of electron energy loss and polarized X-ray absorption spectroscopy. CuGeO₃ shows a surface charge transfer gap of about 3.0±0.3 eV. The unoccupied oxygen derived density of states, as probed by X-ray absorption at the O 1s edge, is in good agreement with recent many-body calculations.     

Electron energy loss spectra from polycrystalline Cr and Cr2O3 before and after surface reduction by Ar bombardment

Electron energy loss spectra (ELS) have been obtained from polycrystalline Cr and Cr₂O₃ before and after surface reduction by 2 keV Ar⁺ bombardment. The primary electron energy used in the ELS measurements was systematically varied from 100 to 1150 eV in order to distinguish surface versus bulk loss processes. Two predominant loss features in the ELS spectra obtained from Cr metal at 9.0 and 23.0 eV are assigned to the surface and bulk plasmon excitations, respectively, and a number of other features arising from single electron transitions from both the bulk and surface Cr 3d bands to higher-lying states in the conduction band are also present. The ELS spectra obtained from Cr₂O₃ exhibit features that originate from both interband transitions and charge-transfer transitions between the Cr and O ions as well as the bulk plasmon at 24.4 eV. The ELS feature at 4.0 eV arises from a charge-transfer transition between the oxygen and chromium ions in the two surface layers beneath the chemisorbed oxygen layer, and the ELS feature at 9.8 eV arises from a similar transition involving the chemisorbed oxygen atoms. The intensity of the ELS peak at 9.8 eV decreases after Ar⁺ sputtering due to the removal of chemisorbed oxygen atoms. Sputtering also increases the number of Cr²⁺ states on the surface, which in turn increases the intensity of the 4.0 eV feature. Furthermore, the ELS spectra obtained from the sputtered Cr₂O₃ surface exhibit features characteristic of both Cr⁰ and Cr₂O₃, indicating that Ar⁺ sputtering reduces Cr₂O₃. The fact that neither the surface- nor the bulk-plasmon features of Cr⁰ can be observed in the ELS spectra obtained from sputtered Cr₂O₃ while the loss features due to Cr⁰ interband transitions are clearly present indicates that Cr⁰ atoms form small clusters lacking a bulk metallic nature during Ar⁺ bombardment of Cr₂O₃.     

Hydrogen chemisorption on silicon (100) 2 × 1

Changes in the valence band density of states (DOS) of a (100) silicon surface that accompany he chemisorption of atomic hydrogen onto that surface are deduced from a study of the changes in the L_2,3VV Auger lineshape. Complementary changes in the conduction band DOS are inferred from changes in L_2,3VV-core-level characteristic loss spectra (CLS). The chemisorbed hydrogen layer is identified as the dihydride phase from low energy electron diffraction measurements. Upon hydrogen adsorption the DOS at the top of the valence band decreases and new energy levels associated with the Si-H bonds appear lower in the band. Assuming that the Auger signal from the hydrogen covered sample consists of a superposition of a signal from silicon atoms bonded to hydrogen in the dihydride layer and an elemental-Si signal from the substrate, a N(E) difference spectrum with features due only to the dihydride is obtained by subtracting the background corrected, loss deconvoluted L_2,3VV signal for a clean (100)Si surface rom the corresponding signal for the hydrogen covered surface. Comparisons of the energy position of the major peak in this difference spectrum with that of the main peak in a gas phase silane Si-L_2,3VV spectrum, and of the corresponding Auger energy calculated empirically, indicate a hole—hole interaction energy of ~8 eV for the two-hole final state in the gaseous system and zero for the dihydride surface system. Hydrogen induced changes in the conduction band DOS are less apparent than those of the valence band DOS with only the possibility of a decrease in the DOS at the bottom of the conduction band being inferred from the CLS measurements. Electron stimulated desorption of hydrogen from the dihydride layer is adduced from changes in the Auger lineshape under electron beam irradiation of the surface. Hydrogen induced changes in the near-elastic electron energy loss spectra (ELS) are also reported and compared with previously published ELS results.     

Determination of the surface composition of palladium-nickel alloy film catalysts using Auger electron spectroscopy

Palladium-nickel films evaporated in UHV on room temperature substrates form alloys of good bulk homogeneity as indicated by X-ray diffraction. The average composition of the outermost 3 to 5 atom layers has been determined from the intensities of the high energy 848 eV nickel and 330 eV palladium Auger electrons. This average composition is in close agreement with the bulk composition determined by X-ray diffraction, X-ray fluorescence and atomic absorption spectrophotometry. If the nickel concentration is determined from the intensity of the low energy 61 eV nickel Auger electrons, when the analysis refers more critically to the first 1 to 3 atom layers, then a surface enrichment of palladium is indicated for all alloy compositions. From the decrease in the relative intensities of the low energy and high energy nickel Auger electrons with increasing palladium concentration it may be deduced that the enrichment of palladium in the first atom layer is higher than in the second and third layers and that a complete monolayer of palladium is formed for bulk concentrations of 65 at% or more. The experimental observations are in qualitative agreement with theoretical predictions of surface composition from bulk thermodynamic data. The palladium-nickel alloys form a range of surface compositions which can be controlled by changing the bulk composition and which are useful for studying catalytic activity as a function of composition. The alloy films are stable under electron irradiation in the AES analysis in UHV but air exposed films analysed in a residual pressure of 1.3 microPa water vapour show a decrease in palladium surface concentration on irradiation indicating a diffusion of nickel to the surface to form an overlayer of nickel oxide.