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1.
Approximate molecular orbital calculations have been applied to explain the low CO poisoning effects observed at PtBi2 and PtBi electrodes. The bonding patterns for chemisorption of CO on the surfaces of Pt-Bi bulk alloys and pure Pt surfaces are quite similar. The major difference is not induced through much Pt-Bi bonding, but indirectly, by raising the Fermi level of the system, so that the C-O π* levels become practically filled upon interaction. This results in much lower adsorption energies than in the metallic Pt case, in accordance with experimental data. The calculations also imply C-O bond dissociation on the surface, a phenomenon not supported by experiment. CO adsorption at Pt-Pt bridge site (possible only on PtBi) is favored relative to atop chemisorption.  相似文献   

2.
The specific heats of the Ni2B amorphous system and of its crystal analog were studied in the temperature range 3–270 K. The data obtained permitted us to isolate the contribution due to atomic vibrations from the experimentally measured specific heat, determine the electronic density of states at the Fermi level and the temperature dependence of the characteristic Debye parameter Θ, and to calculate some average frequencies (moments) of the vibrational spectrum. The electronic density of states at the Fermi level increases under amorphization. An analysis of the temperature dependence of the lattice specific heat showed that amorphization brings about a substantial growth in the density of vibrational states at low frequencies, whereas the spectrum-averaged and rms frequencies change very little, which is in good agreement with neutron diffraction measurements.  相似文献   

3.
Qualitative changes are observed in the character of the surface electronic structure accompanying the adsorption of potassium on a Si(111) 7×7 surface. The metallic conductivity of the Si(111)7×7 surface is destroyed at the very early stages of adsorption. A new band induced by the adsorption of potassium is observed below the Fermi level. It is found that the K/Si(111)7×7 interface is semiconducting right up to saturating coverage. A surface transition from an insulating into a metallic state, accompanied by pinning of the Fermi level, is observed in the region of saturating coverage. Metallic conductivity arises in the adsorbed potassium layer as a result of the development of an induced surface band at the Fermi level. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 1, 27–30 (10 July 1997)  相似文献   

4.
Using a scanning tunneling microscope, we found metastable upright NO on Cu(110) with the 2π* molecular resonance at the Fermi level. Upon heating above 40 K, it converts to a bent structure with the loss of molecular resonance. By manipulating the distance between two upright NO, we controlled the overlap between 2π* orbitals and observed its splitting below and above the Fermi level, thus visualizing the covalent interaction between them.  相似文献   

5.
In this work, we report density functional theory calculations exploring H2S dissociation on the (1 1 1) surfaces of Pd, Cu, Ag, Au, and various bimetallic surfaces consisting of those metals. To understand the contributions of lattice strain and electronic ligand effects, the thermodynamics of each elementary dissociation step were explored on model bimetallic surfaces, including PdMPd sandwiches and Pd pseudomorphic overlayers, as well as strained Pd(1 1 1) surfaces and homogeneous Pd3M alloys. Sulfuric (H2S, SH, and S) adsorption energies were found to correlate very well with lattice constant, which can be explained by the strong correlation of the lattice constant with d-band center, Fermi energy, and density of states at the Fermi level for strained Pd(1 1 1) surfaces. Compressing the Pd lattice shifts the d-band center away from the Fermi level, lowers the Fermi energy, and reduces the density of d-states at the Fermi level. All three effects likely contribute to the destabilization of sulfuric adsorption on Pd alloys. Introducing ligand effects was found to alter the distribution of the d-states and shift the Fermi level, which eliminates the correlation of the d-band center with the density of states at the Fermi level and the Fermi energy. As a result, the d-band center by itself is a poor metric of the H2S reaction energetics for bimetallic surfaces. Furthermore, combining strain with ligand effects was found to lead to unpredictable alterations of the d-band. Therefore, adsorption of H2S, SH, and S on PdMPd surfaces do not accurately predict adsorption on Pd3M surfaces.  相似文献   

6.
闫隆  张永平  彭毅萍  庞世谨  高鸿钧 《物理学报》2001,50(11):2132-2136
利用超高真空扫描隧道显微镜研究了室温条件下Ge在Si(111)7×7表面上初期吸附过程.在Ge所形成团簇中存在一个临界核.这些Ge团簇的吸附中心总是在三个增原子所围成的区域中.它们的电子结构具有类似半导体的性质,即其局域态密度在远离费米面的能级处很大,而在费米面附近的能级处非常小. 关键词: 扫描隧道显微镜 Si(111)7×7表面 Ge团簇  相似文献   

7.
本文基于密度泛函理论的第一性原理方法了计算了Rb、O和H吸附石墨烯纳米带的差分电荷密度、能带结构、分波态密度和介电函数,调制了石墨烯纳米带的电子性质和光学性质,给出了不同杂质影响材料光学特性的规律.结果表明本征石墨烯纳米带为n型直接带隙半导体且带隙值为0.639 eV;Rb原子吸附石墨烯纳米带之后变为n型简并直接带隙半导体,带隙值为0.494eV;Rb和O吸附石墨烯纳米带变为p型简并直接带隙半导体,带隙值增加为0.996eV;增加H吸附石墨烯纳米带后,半导体类型变为n型直接带隙半导体,且带隙变为0.299eV,带隙值相对减小,更有利于半导体发光器件制备.吸附Rb、O和H原子后,石墨烯纳米带中电荷密度发生转移,导致C、Rb、O和H之间成键作用显著.吸附Rb之后,在费米能级附近由C-2p、Rb-5s贡献;增加O原子吸附之后,O-2p在费米能级附近贡献非常活跃,杂化效应使费米能级分裂出一条能带;再增加H原子吸附之后,Rb-4p贡献发生蓝移,O-2p在费米能级附近贡献非常强,费米能级分裂出两条能带.Rb、O和H的吸附后,明显调制了石墨烯纳米带的光学性质.  相似文献   

8.
利用密度泛函理论和广义梯度近似研究镍吸附在Al(111)表面。在覆盖率为0.25ML下,分析了Ni吸附在Al(111)表面的面心立方洞位、六角密排洞位、顶位和桥位四个高对称位的原子结构和吸附能。比较不同高对称位的吸附能发现,六角密排洞位的吸附能最大,是5.76 eV,是最稳定的吸附位置。详细讨论了两个最低能量结构-三重洞位的电子结构、功函数、表面偶极距和Ni-Al键的特性。在费米能级附近,Ni-3d和Al-3s,3p轨道产生杂化,形成金属间化合键。由于吸附导致双金属体系表面偶极距和功函数的变化。我们发现:Ni原子与Al(111)表面原子间成建主要是共价键,没有表现出明显的静电荷跃迁,相应的产生非常小的表面偶极距。与面心立方洞位相比,六角密排洞位在费米能级附近产生较低的态密度,在键态附近产生较大的杂化。  相似文献   

9.
Using angle-resolved photoemission, we have identified a new surface state on Ir(332), which can be unambigously associated with step sites. This state is located near the Fermi level and can be distinguished from a terrace-related state by preferential adsorption of hydrogen on the rows of step atoms. Terrace and step atoms are shown to exhibit different 4f-core level binding energies, a fact which can be used to independently monitor preferential adsorption.  相似文献   

10.
11.
Angle-resolved photoemission measurements are used to compare the room temperature adsorption of benzene and chlorobenzene on a Pt{001} surface. From the polar emission angle dependence of the intensities, the molecular orientation is determined. The chlorine 3p “lone-pair” electrons are identified at 5.5 eV below the Fermi level by comparison with gas phase spectra. The changes in the work function on adsorption are noted for each species.  相似文献   

12.
He II-ultraviolet photoelectron spectra (hv = 40.8 eV) from a carbon monoxide layer adsorbed on a Cu(111) surface exhibit two peaks at 8.5 and 11.6 eV below the Fermi level and a weaker maximum centered at about 13.5 eV. The emission from the Cu d-band is markedly suppressed after adsorption. The results are discussed in terms of the recent models for assigning the UPS peaks observed after adsorption of CO on transtion metals  相似文献   

13.
Oxygen adsorption on the α-Mo2C(0 0 0 1) surface has been investigated with X-ray photoelectron spectroscopy and valence photoelectron spectroscopy utilizing synchrotron radiation. It is found that oxygen adsorbs dissociatively at room temperature, and the adsorbed oxygen atoms interact with both Mo and C atoms to form an oxycarbide layer. As the O-adsorbed surface is heated at ≧800 K, the C-O bonds are broken and the adsorbed oxygen atoms are bound only to Mo atoms. Valence PES study shows that the oxygen adsorption induces a peculiar state around the Fermi level, which enhances the emission intensity at the Fermi edge in PES spectra.  相似文献   

14.
The intensity of metastable helium (He*) atoms which survive during the scattering from water- and benzene-adsorbed Cu(1 0 0) surfaces was measured. The survival probability (SP) of He* was found to be sensitive to the electronic states at around the Fermi level, which is derived from the adsorbate/metal hybridization and extend toward the vacuum. The SP is likely to depend largely on the kinetic energy of the He* atoms. The kinetic energy dependence can be understood on the basis of the He* decay mechanism. Metastable-atom deexcitation spectroscopy (MDS) and surface electronic structure calculation have been used for discussing the results for the He* SP.  相似文献   

15.
Evolution of G-band modes of single metallic carbon nanotubes with the Fermi level shift is examined by simultaneous Raman and electron transport studies. Narrow Lorentzian line shape and upshifted frequencies are observed near the van Hove singularities. However, all G modes soften and broaden at the band crossing point. The concurrent appearance of an asymmetric Fano line shape at this point indicates that phonon-continuum coupling is intrinsic to single metallic tubes. The apparent Lorentzian line shapes of as-synthesized metallic tubes are induced by O2 adsorption causing the Fermi level shift.  相似文献   

16.
Ultraviolet photoelectron spectroscopy (UPS) has been used to study the chemisorption of CO, O2, and H2 on platinum. Three single crystal surfaces ((111), 6(111) × (100), and 6(111) × (111)) and two polycrystalline surfaces were studied. These studies yielded three important results. First, the most dominant change in the Pt valence band upon gas adsorption was a decrease in the height of the peak immediately below the Fermi level. This decrease was nearly identical for all three gases studied. Second, CO adsorption resulted in the formation of a resonance state ~8 eV below the Fermi level which was attributed to CO molecular orbitals. In contrast, no dominant resonance states were observed for adsorbed O or H. The lack of an O resonance state on platinum is in contrast to the results observed for O adsorbed on Fe and Ni and suggests important differences between the OPt chemisorption bond and the OFe and ONi chemisorption bonds. Finally, adsorption of CO at steps or defects led to a decrease in work function while its adsorption on terraces led to an increase in work function. For H, adsorption at steps led to an increase in work function while adsorption on terraces led to a decrease in work function. The adsorption of O led to an increase in work function on all of the surfaces studied.  相似文献   

17.
基于密度泛函理论(DFT)的广义梯度近似(GGA),本文对本征石墨烯以及掺杂Fe,Co,Ni石墨烯的几何结构和电子性质进行了优化计算,并计算了C_2H_4在本征石墨烯以及掺杂石墨烯表面的吸附过程,讨论了体系的吸附能、稳定性、DOS及掺杂对键长的影响.结果表明C_2H_4在本征石墨烯B位的吸附和掺杂石墨烯的吸附为化学吸附,在本征石墨烯T和H位的吸附为物理吸附;掺杂后石墨烯的比表面积增大,与本征石墨烯相比,掺杂使费米能级附近的态密度积分显著提高,表明掺杂石墨烯的电导性会发生变化,从而影响对C_2H_4的气敏度..C_2H_4在Fe、Co、Ni分别掺石墨烯的最佳吸附位为T位、H位和B位;掺杂Fe,Ni后体系的吸附能力显著提高,且掺杂Ni时体系的吸附能力最好.  相似文献   

18.
This paper reports on a study of the adsorption of CO molecules on the surface of ytterbium nanofilms of different thicknesses, which were sublimed on Si(111)7 × 7 at room temperature. Dependences of two types were investigated: the surface concentration of adsorbed molecules vs. CO dose expressed in langmuirs and the work function of films vs. CO dose. It was shown that the behavior of these dependences is mediated by size effects and Friedel oscillations generated by the ytterbium-silicon interface. Both effects exert an influence on the binding of CO molecules to the surface. At low molecule concentrations, this binding is effected through lone electron pairs localized at the carbon ends of the molecules. These electrons form a donor-acceptor bond to the vacant 5d level of the metal, with the level dropping below the Fermi level. At high CO molecule concentrations, the pattern becomes more complex; indeed, the enhanced Coulomb interaction gives rise to a partial transfer of electrons from the 5d level to the vacant 2π* orbital of CO molecules.  相似文献   

19.
《Surface science》1996,366(1):L685-L688
The adsorption and desorption of water on UHV-cleaved GaAs(110) surfaces was studied using synchrotron-excited photoelectron spectroscopy. Water was adsorbed at T = 100 K. Desorption was studied during heating to room temperature. At low coverages, dissociated species are observed followed by molecular adsorption. Molecular water is desorbed at T = 160 K. The dissociated species are also mainly desorbed after heating to room temperature. The chemical changes are accompanied by substrate binding-energy shifts, reflecting the movement of the Fermi level at the surface.  相似文献   

20.
The reaction mechanisms of Al(CH3 )3 (TMA) adsorption on H-passivated GeSi(100)-2 × 1 surface are investigated with density functional theory. The Si-Ge and Ge-Ge one-dimer cluster models are employed to represent the GeSi(100)-2 × 1 surface with different Ge compositions. For a Si-Ge dimer of a H-passivated SiGe surface, TMA adsorption on both Si-H^* and Ge-H^* sites is considered. The activation barrier of TMA with the Si-H^* site (1.2eV) is higher than that of TMA with the Ge-H^* site (0.91 eV), which indicates that the reaction proceeds more slowly on the Si-H^* site than on the Ge-H^* site. In addition, adsorption of TMA is more energetically favorable on the Ge-Ge dimer than on the Si-Ge dimer of H-passivated SiGe.  相似文献   

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