NO在清洁和Cs覆盖的Ru(100)表面上吸附的热脱附谱

用热脱附谱等方法研究了NO分别在清洁和Cs覆盖的Ru(1010)表面上的吸附.结果表明:存在两种NO分子吸附态(a1,a2),脱附温度分别处于325℃和550℃附近.Cs的存在增加了Ru(1010)表面上a2态的吸附位置,提高了该态的脱附温度.Cs在Ru(1010)表面上的存在同时促进了吸附NO分子的分解.NO在Ru(1010)表面上分解后形成吸附O原子和N原子.N原子复合以N2在约500℃附近脱附,同时Cs的存在也促进了N2O的形成.在Cs覆盖的Ru(1010)表面上,N2O的脱附温度约在425℃.     

CO分子与碱金属原子在Fe(110)表面上的相互作用

本文介绍了CO分子分别与K原子或Na原子在Fe(110)表面上共吸附的研究。角分辨率紫外光电子能谱(ARUPS)的结果表明,碱金属原子在Fe(110)表面上的存在,紫外光电子能谱中出现了结合能低于通常CO分子1π能级的新峰。该峰位于费密能级以下6.3eV处,是C0在碱金属影响下电子结构改变的结果。该峰的出现对应着CO分子处于C—O键明显减弱的状态。偏振紫外光电子能谱的研究表明:6.3eV处的谱峰联系的电子轨道有一个对称平面和一个反对称平面,分别平行于<001>晶向和<110>晶向。CO分子轨道的对称性不因 关键词：     

tetracene 分子在Ru(1010)表面的吸附结构及其电子态研究

利用紫外光电子能谱(UPS)、角分辨紫外光电子能谱(ARUPS)和扫描隧道显微镜(STM)等方法研究了tetracene分子在Ru(1010)表面上吸附的电子态，吸附位置和吸附取向.UPS实验显示，与tetracene分子有关的光电子谱峰在费米能级以下2.1, 3.5, 4.8, 6.0, 7.1和9.2 eV处；ARUPS 结果表明，tetracene分子的分子平面基本平行于衬底表面；从STM图像中可以看到tetracene分子的长轴沿［0001］和［1210］两个晶向.基于密度泛函理论的从头算计算证实了上述结论.当分子长轴沿［0001］晶向时，分子中心位置在衬底表面的“短桥位”上，当分子长轴沿［1210］晶向时，分子中心位置在衬底表面的“四原子中心空位”上. 关键词： tetracene分子 Ru(1010)表面 吸附结构 吸附电子态     

CO在有K沉积的W(100)面上吸附的角分辨紫外光电子能谱

在不同K覆盖度的W(100)面上吸附CO的Hel紫外光电子能谱研究表明:α和β态的CO由于K的影响,吸附状态发生改变,与CO分子态(α态)有关的5σ/1π分子轨道能级随K覆盖度的增加,结合能位置从8.6eV移到9.3eV,反映K出现后,衬底对α-CO分子反施的增强。在与CO分解态(β态)有关的谱峰位置上(结合能为5.5eV)出现两个离散的谱峰,一个在6.0eV左右,另一个在5.2eV左右。其中结合能在5.2eV左右的谱峰强度随K的覆盖度增加而增大,它的能量位置与O在K覆盖的W(100)面上吸附时的能级位置 关键词：     

OPCOT在Ru(0001)表面上的紫外光电子能谱研究

采用紫外光电子能谱,研究了新型有机发光材料八芳基环辛四烯(OPCOT)在金属Ru(0001)表面上的电子结构,以及它们之间的相互作用.位于费米能级以下43,69,93和114eV处的4个谱峰分别来自于OPCOT材料中苯环的πCC,σCC,σCH和σHH轨道,位于30eV处的谱峰反映了8个苯环聚合后具有π轨道特性的C—C键.OPCOT材料的价带顶位于费米能级以下25eV处,OPCOT材料在Ru(0001)表面上的功函数为395eV.150℃以下,OPCOT材料可以在Ru(0001)表面稳定存在.随温度的升高,OPCOT材料主要以脱附的形式减少 关键词： 八芳基环辛四烯 光电子能谱 价电子结构 脱附     

乙烯在Ru（1010）表面价带电子特性研究

在200K以下乙烯(C2H4)可以在Ru（1010）表面上以分子状态稳定吸附,200K以上乙烯发生了脱氢分解反应生成乙炔(C2H2)。乙烯分解生成乙炔后,σCC和σCH分子轨道能级向高结合能方向分别移动了0．5和1.1eV。偏振角分辨紫光电子谱（ARUPS)结果表明：在RM（1010）表面上,乙烯和脱氨反应后生成的乙炔分子的C—C键轴都不平行于表面,而是沿表面(0001)晶向倾斜。     

C2H2,C2H4与K在Ru（1010）表面上共吸附的UPS研究

利用紫外光电子谱(UPS)对乙烯(C2H4)和乙烯(C2H2)气体在Ru(1010)表面的吸附及与K的共吸附进行了研究,实验结果表明：当衬底温度超过200K,乙烯即发生脱氢反应后,σCH和σCC能级均高结合方向移动．在室温下、σCH和σCC能级位置与乙炔在Ru(1010)表面的吸附时的分子能级完全一致．乙烯发生脱氢反应后的主要产物为乙炔。衬底温度从120K升到室温,Ru(1010)表面上乙炔的σCH和σCC能级均未发现变化．室温下乙炔仍然可以在Ru(1010)表面以分子状态稳定吸附．在有K的Ru(1010）表面上．室温时σCH谱峰几乎消失．碱金属K的存在促进了乙炔的分解．     

苝四甲酸二酐薄膜电子结构的同步辐射共振光电子能谱研究

利用基于同步辐射的近边X射线吸收精细结构谱(NEXAFS)和共振光电子谱(RPES)研究了苝四甲酸二酐分子(PTCDA)薄膜的电子结构.碳K边NEXAFS谱中能量小于290 eV的四个峰对应于PTCDA分子不同化学环境碳原子1s电子到未占据分子轨道的共振跃迁.RPES谱中观察到共振光电子发射和共振俄歇电子发射导致的共振峰结构,以及二次谐波激发的碳1s信号.根据电子动能对入射光能量的依赖性分别对三类峰结构进行了归属.同时,发现PTCDA分子轨道共振光电子峰的强度具有光子能量依赖性.这种能量选择性共振增强效应是由于PTCDA分子轨道空间分布差异导致的.共振俄歇峰主要源于高结合能(4.1 eV)分子轨道能级电子参与的退激发过程.明确RPES实验谱图中各个峰结构的起源有助于准确利用基于RPES的芯能级空穴时钟谱技术定量估算有机分子/电极异质界面处电子从分子未占据轨道到电极导带的超快转移时间.     

CO与K在Fe(110)面上共吸附的角分辨紫外光电子谱

用角分辨偏振紫外光电子谱对CO与K在Fe(110)表面上共吸附进行了研究。CO与K共吸附的Hel紫外光电子谱与清洁表面上CO的结果相比,在结合能为6.3eV处出现了一个新的谱峰。偏振紫外光电子谱的分析表明:相关的初态有一对称面,此面平行于衬底〈001〉方向。Hell紫外光电子谱中,CO的4σ态(4α₁)强度随入射角改变的结果表明CO依然近似于直立在有K覆盖的Fe表面上。 关键词：     

Ag(110)表面吸附酞菁铜分子的紫外光电子谱研究

用紫外光电子能谱(UPS)研究了酞菁铜分子在Ag(110)单晶表面上的吸附，随着酞菁铜分子覆盖度增加，衬底Ag的3d电子信号逐渐减弱，在此能带区域出现两个新的谱峰，这两个与吸附有机分子轨道有关的谱峰的束缚能分别为4.45 和6.36 eV.随着覆盖度的增加，在结合能为1.51和9.20 eV处又出现了两个谱峰，它们同样来自吸附有机分子的轨道.随着覆盖度的继续增加，上述四个谱峰的强度逐渐增加，其能量位置均发生了明显的偏移.根据角分辨光电子能谱的实验结果，酞菁铜分子的分子平面基本与衬底表面平行.密度泛函理论计     

富镧混合稀土-镍贮氢材料CO,O2和H2O中毒的表面特征

本文用UPS,XPS研究了贮氢材料MlNi₅(Ml=La,Ce,Pr,Nd)的CO,O₂和H₂O的中毒,在UPS谱中,我们观察到在E_F以下峰α(0.3eV)和峰b(1.2eV)强度随中毒气体暴露量增加有显著变化,并向低动能端位移,逐渐形成肩峰,与此同时,峰c(6eV)和峰d(9.5eV)的强度随暴露量增加而增加,并有能量位移,配合XPS分析,分别确定相应的化学态。氧中毒后的MlNi₅,经300℃加氢还原,从UPS谱可以看到峰α,b强度增加;H₂O和CO中毒后,在超高真空条件下,分别经300℃加热处理,和Ar⁺剥离方法,均获得类似的效果,XPS分析进一步证实了这些结果。实验给出了贮氢材料MlNi₅中过渡金属镍的d电子与气体自由分子轨道间电荷转移的信息,为在实际应用中认识此类贮氢合金的表面催化中毒和再生提供了依据。 关键词：     

Valence band and band gap photoemission study of (1 1 1) In2O3 epitaxial films under interactions with oxygen, water and carbon monoxide

Synchrotron radiation ultraviolet photoemission experiments at photon energies of 150 and 49 eV were performed on an epitaxial layer of (1 1 1) In₂O₃ with good crystallinity as established by a standard scanning probe and diffraction methods. Valence band (VB) and band gap photoemission spectra were monitored under separate oxygen, water and carbon monoxide exposures (100 L) at different activation temperatures within the range utilized for chemiresistive gas sensors (160-450 °C). Large changes in photoemission response within the whole VB were observed for all gases. Regular shifts of the valence band edge relative to the Fermi energy were found under gas exposures on two kinds of surface (partially reduced or partially oxidized), and are interpreted as changes of surface potential. Treatments in oxygen resulted in upward band bending (∼0.5 eV at T = 320 °C). Regardless of activation temperature, treatments in water resulted in downward band bending, but with small changes (<0.1 eV). Reduction properties of carbon monoxide were observed only at high temperatures of T ? 370 °C. At temperatures of 160 and 250 °C unusual “oxidizing” behavior of CO was observed with upward band bending of ∼0.7 eV (160 °C). Oxidizing and reducing effects of the gas interactions with the (1 1 1) In₂O₃ surface in all cases were accompanied by a corresponding behavior, i.e., a decrease or increase in photoemission response from so-called defect states in the band gap near the top of the valence band. The increases of photoemission within a band gap with maxima at binding energies (BE) of 0.4 (O₂-induced peak) and 1.0 eV (CO-induced peak) were, respectively, found for interactions with O₂ and CO for low temperatures (T = 160 and 250 °C). These responses were ascribed to acceptor-like electronic levels of O₂ and CO chemisorption states, respectively. A definite split of the top VB peak (BE ∼ 4.0 eV) was found under CO dosing at 160 °C. Established knowledge of the CO interaction with the (1 1 1) In₂O₃ surface explains earlier revealed acceptor-like behavior of In₂O₃ film conductivity during CO detection at operational temperatures lower than 250 °C through the formation of acceptor-like electronic levels of adsorbed CO molecules.     

An X-ray photoelectron spectroscopic study of the adsorption of N2, NH3, NO,and N2O on dysprosium

The adsorption of N₂, NH₃, NO, and N₂O onto clean polycrystalline dysprosium at 300 and 115 K and the changes undergone by the adsorbed species upon heating from 115 K have been investigated using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). At 115 K, N₂ adsorbs dissociatively, vielding two peaks in the N 1s region at 396.2 and 398.2 eV corresponding respectively to a nitride and to chemisorbed nitrogen N(a). No peaks corresponding to molecularly adsorbed N₂ (BE 400.2 eV [10]) were observed. Upon heating the sample the N(a) is converted into the nitride species, as evidenced by a decrease in the 398.2 eV peak and a corresponding increase in the 396.2 eV peak. At a warm-up temperature of 300 K, the N(a) species accounts for only ～10% of the total nitrogen on the surface. Ammonia adsorbed at 115 K shows three distinct peaks, at 401.7, 399.3 and 396.2 eV, corresponding to molecular, partly dissociated, and completely dissociated (nitride) ammonia. Upon heating multilayer ammonia to 175 K, it desorbs to leave predominantly the peak corresponding to the partly dissociated species. Upon further heating the molecular and partly dissociated ammonia is converted into the nitride species. At 400 K only nitride-type nitrogen remains on the surface. The adsorption of NO and N₂O at 115 K is predominantly dissociative. NO has N 1s peaks at 403.1 and 396.3 eV corresponding possibly to molecularly adsorbed NO, and to nitride species. After N₂O adsorption there is very little nitrogen on the surface. Adsorption of N₂ and NO at 300 K yields only the peak at 396.2 eV, whereas NH₃ yields, in addition to this peak, a small intensity (～20%) of the peak at 398.2 eV (partly dissociated ammonia).     

Valence band states of semi-magnetic semiconductors: Cd1-xMnxTe

Valence band electron states of Cd_1-xMn_xTe mixed crystals were determined over the composition range 0?x?0.7 by ultra-violet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). A peak at 3.5 eV binding energy (BE) whose magnitude increases with the manganese mole fraction x was identified as originating from the Mn 3d⁵ level. A previously reported structure at 6.5 eV BE was also observed for x>0.4; it is, however, believed to be a satellite of the 3.5 eV peak originating from a shake-up process.     

CO adsorption on oxygen-modified molybdenum surfaces

Structures of carbon monoxide layers on the oxygen-modified Mo(1 1 0) and Mo(1 1 2) surfaces have been investigated by means of density-functional (DFT) calculations. It is found that CO molecules adsorb at hollow sites on the O/Mo(1 1 0) surface and nearly atop Mo atoms on the O/Mo(1 1 2) surface. The favorable positions for adsorption are shown to be near protrusions of electron density above the Mo surface atoms. The presence of oxygen on the molybdenum surface significantly reduces the binding energy of the CO molecule with the substrate; on the oxygen-saturated Mo(1 1 0) surface, the adsorption of CO is completely blocked. The calculated local densities of states (LDOS) demonstrate that the O 2s peak for O adsorbed on Mo(1 1 0) surface is at −19 eV (with respect to the Fermi level), while for the oxygen atom of an adsorbed CO molecule the related 3σ molecular orbital gives rise to a peak at −23 eV. This difference stems from the bonding of the O atom either with Mo surface for adsorbed O or with C atom in adsorbed CO, and therefore the position of the O 2s peak in photoemission spectra can serve as a convincing argument in favor of either the presence or absence of the CO dissociation on Mo surfaces.     

Reduced stretch vibration frequency for CO on Na covered Cu(100)

When Na is coadsorbed with CO on Cu(100), EELS show a peak at around 0.17 eV loss energy in addition to the peak at 0.26 eV which is characteristic of CO on Na-free Cu(100). The low energy peak is ascribed to CO molecules adsorbed near Na atoms. The appearance of both the shifted and unshifted loss peaks demonstrates the local nature of the alkali-CO interaction for the present system.     

Molecular orbital study of co chemisorption and oxidation on a Pt(111) surface

A molecular orbital study was made, using an atom superposition and electron delocalization (ASED) technique, of the structures and energy levels of CO on Pt(111) surface. CO is predicted to be preferentially adsorbed at a height of 2.05 Å from the surface at a 1-fold position with the carbon end down. The calculated binding energy (1.7 eV) is in good agreement with the recent experimental result (1.5 eV) of Campbell et al. Calculated binding energies for bridging (1.3 eV) and high coordinate (1.1 eV) sites are predicted to be smaller in magnitude. Calculated results are used to discuss the ordering of energy levels of adsorbed CO. The interaction between CO (adsorbed) and O (adsorbed) has been studied to estimate the energy of activation for the oxidation of CO on Pt(111) surface. The calculated activation energy (1.6 eV) is in reasonable agreement with the recent experimental result (1 eV) of Campbell et al. The Langmuir-Hinshelwood mechanism is found to be favored. We predict CO₂ bonds vertically.     

Untersuchung über den einfluss von adsorbierten gasen auf die elektronen-energieverlust-spektren einer Ni(110)-oberfläche

Electron energy loss spectra on a (110) nickel surface exhibit characteristic changes upon adsorption of H₂, CO and O₂. The clean surface shows only the surface and bulk plasmon losses at 8 eV and 18 eV respectively. Adsorption of CO produces two new loss peaks at 13.5 eV and 5.5 eV. Loss peaks due to hydrogen adsorption at 15 eV and 7.5 eV show a strong correlation with the well known adsorption characteristics of this system. The oxygen induced losses are different for chemisorbed O on Ni and NiO. In any case the chemisorption-induced losses are well established for primary energies below 120eV. In the loss spectra with higher excitation energies only a drastic decrease of the surface plasmon loss peak-height is visible. If the new losses can be attributed to one-electron excitations from molecular orbital levels due to the chemisorption bond, with assumptions of the final state of the excited electron a determination of the postition of these levels can be made. In case of CO and H₂ reasonable results are evaluated.     

Collision-induced migration of CO on Pt(9 9 7) surface

Lateral displacement of adsorbates induced by collisions with energy-controlled rare gas atoms was examined in an ultra high vacuum chamber using Fourier-transform infrared (FTIR) spectroscopy and a supersonic molecular beam apparatus. A stepped Pt(9 9 7) surface was exposed to CO molecules and subsequently to energy-controlled Ne or Ar atoms. There was no change in the CO stretching mode region of the FTIR spectrum of the Pt(9 9 7) surface after Ne atoms having an average translational energy of 0.23 eV were collided with it. However, when Ne atoms having an average translational energy of 0.56 eV were collided with the surface, the intensity of the peak assigned to the CO stretching mode at terrace sites decreased, while that at step sites increased with increasing the exposure to the Ne atoms. This is the demonstration of collision-induced migration, showing that CO molecules adsorbed at the terrace sites migrate laterally to the step sites upon collision with high-energy Ne atoms. In addition, the experimental results demonstrate the existence of an additional energy barrier for jumps across the steps. This investigation demonstrates an advantage of using a molecular beam for studying adsorbate migration.