Evidence of subsurface oxygen vacancy ordering on reduced CeO2(111)

Surface and subsurface oxygen vacancies on the slightly reduced CeO(2)(111) surface have been studied by atomic resolution dynamic force microscopy at 80 K. Both types of defect are clearly identified by the comparison of the observed topographic features with the corresponding structures predicted from recent first-principles calculations. By combining two simultaneously acquired signals (the topography and the energy dissipated from the cantilever oscillation), we are able to unambiguously locate subsurface oxygen vacancies buried at the third surface atomic layer. We report evidence of local ordering of these subsurface defects that suggests the existence of a delicate balance between subtle interactions among adjacent subsurface oxygen vacancy structures.     

Rh在CeO_2(111)表面吸附的第一性原理研究

采用基于广义梯度近似的投影缀加平面波(Projector augmented wave)赝势和具有三维周期性边界条件的超晶胞模型,用第一原理计算方法,计算并分析了Rh在CeO_2(111)表面吸附所形成的Rh/CeO_2(111)界面体系的吸附能,价键结构和局域电子结构.考虑了Rh在不同吸附位置的吸附情况.结果表明:1)Rh在CeO_2(111)面有较大的吸附能,表明Rh与CeO_2(111)面有较强的相互作用,而且Rh在位于表面O的三度位,且位于次层氧的顶位的吸附最强;2)Rh的4d态同衬底O的2p态有明显的杂化作用,这是Rh同CeO_2较强作用的主要原因;3)Rh被CeO_2(主要是Rh的次近邻的Ce)氧化为Rh~(3+),并伴随着Ce~(4+)→Ce~(3+)反应的发生.     

Pd与CeO2(111)面的相互作用的第一性原理研究

采用基于广义梯度近似的投影缀加平面波(projector augmented wave) 赝势和具有三维周期性边界条件的超晶胞模型,用第一性原理计算方法,计算并分析了Pd在CeO2(111)面上不同覆盖度时的吸附能,价键结构和局域电子结构. 考虑了单层Pd和1/4单层Pd两种覆盖度吸附的情况. 结果表明:1)在单层吸附时,Pd的最佳吸附位置是O的顶位偏向Ce的桥位;在1/4单层吸附时,Pd最易在O的桥位偏向次层O的顶位吸附.2) 单层覆盖度吸附时,吸附原子Pd之间的作用较强;1/4单层覆盖度吸附时,同层吸附的Pd之间的几乎没有相互作用. 同时在低覆盖度吸附时,Pd和CeO2衬底的相互作用较高覆盖度时强.3) Pd的吸附只对其近邻的衬底原子结构有明显影响.4) Pd在CeO2衬底上吸附后,Pd和CeO2衬底的活性增强,并可能在Pd与CeO2界面处形成活性中心. 以上结果有助于人们对三元催化剂中Pd与CeO2的协同作用机理的理解.     

STM characterisation of organic molecules on H-terminated Si(111)

We present the first high resolution STM images of organic molecules on the technological important hydrogen terminated silicon surface. Ordered layers of PTCDA and PTCDI were prepared on this surface by organic molecular beam epitaxy. The submolecular contrast of these molecules on Si(111)/H obtained in the high resolution images agrees with the corresponding images on HOPG and MoS₂ substrates.     

Manipulation and control of a single molecular rotor on Au (111) surface

Three different methods are used to manipulate and control phthalocyanine based single molecular rotors on Au (111) surface: (1) changing the molecular structure to alter the rotation potential; (2) using the tunnelling current of the scanning tunnelling microscope (STM) to change the thermal equilibrium of the molecular rotor; (3) artificial manipulation of the molecular rotor to switch the rotation on or off by an STM tip. Furthermore, a molecular `gear wheel' is successfully achieved with two neighbouring molecules.     

Initial stage of adsorption of octithiophene molecules on Cu(111)

The initial stage of the adsorption of octithiophene (8T) molecules on a Cu(111) surface is investigated using a scanning tunneling microscope at room temperature. We find a characteristic molecular chain structure of 8T molecules on a terrace of the Cu(111) surface, which has not been reported so far for adsorption of oligothiophene molecules on metal surfaces. Up to the adsorption of 0.26 monolayer (ML), 8T molecules in the molecular chain align with their long axis parallel to the Cu<11-2> direction. With increasing coverage, there appear 8T molecules that align with their long axis parallel to the Cu<110> direction. The appearance of different molecular orientations is understood by the decrease of the number of the adsorption sites for extending the molecular chains. Fragments of 8T molecules, such as single thiophene molecules, are also observed in this work. They are trapped only at the step edges of the Cu(111) surface at the beginning and later trapped in a small Cu(111) region surrounded by 8T molecules.     

Diffusion and pair interactions of CO molecules on Pd(111)

The diffusion and interactions of CO molecules on Pd(111) were studied by scanning tunneling microscopy. By following the random walk motion of individual molecules as a function of temperature, an activation energy barrier for diffusion of 118 +/- 5 meV was determined. The interaction between CO molecules was found to be repulsive for pairs separated by one or two Pd(111) lattice distances, and weakly attractive at a separation of sqrt[3].     

Two-dimensional self-assembly of DNA base molecules on Cu(111) surfaces

We present scanning tunneling microscope images of the self-assembled nucleic-acid base molecules on the surfaces of Cu(111). The images reveal that the chemical inertness of the Cu(111) substrate allows the molecules to diffuse over the surface to self-assemble themselves spontaneously into their own unique structure: adenine into one-dimensional (1D) molecular chains, thymine into 2D islands, guanine into 2D square lattices, and cytosine into 1D zig-zag molecule-cluster networks. We find that molecular orbital calculations reproduce some of the observed self-assembly, and suggest that base-base interaction induced by hydrogen bonding is essential to this phenomenon.     

Leakage of O2 precursor molecules from inert hydrogen islands on a Pt(111) surface

We have observed, using infrared spectroscopy, that the precursor-mediated O2 chemisorption on the clean and the partially hydrogen-covered Pt(111) surfaces exhibits opposite temperature dependencies above the temperature for stable O2 physisorption. While the chemisorption probability on the clean surface increases with increasing temperature due to thermal activation of the precursor, it decreases on the partially hydrogen-covered surface which we suggest is due to a general loss of the mobile precursor molecules by thermal desorption from chemically inert hydrogen islands.     

Structure and bonding of water on Pt(111)

We address the adsorption of water on Pt(111) using x-ray absorption, x-ray emission, and x-ray photoelectron spectroscopy along with calculations in the framework of density functional theory. Using the direct relationship between the electronic structure and adsorbate geometry, we show that in the first layer all the molecules bind directly to the surface and to each other through the in-layer H bonds without dissociation, creating a nearly flat overlayer. The water molecules are adsorbed through alternating metal-oxygen (M-O) and metal-hydrogen (M-HO) bonds.     

Organizing C60 molecules on a nanostructured Au(111) surface

We have studied, using scanning tunneling microscopy, the adsorption of C₆₀ molecules on a nanostructured Au(111) surface consisting of artificially created two-dimensional cavities. These cavities, one atomic layer deep, are found to be effective as molecular traps at room temperature. Gold atoms at step edges are found to respond to the adsorption of C₆₀ molecules and gross faceting is observed for steps connected with R30° oriented C₆₀ molecular islands. Structural models are proposed to establish the step structures related to all three types of molecular islands.     

Interactions of CO molecules adsorbed on oxidised Cu(111) and Cu(110)

Reflection absorption infrared spectroscopy has been used in conjunction with LEED and surface potential measurements to study low temperature CO adsorption on the oxidised Cu surfaces Cu(111)O|$\text{3}\text{2}\text{?}\text{2}$|, Cu(110)O(2 × 1) and Cu(110)Oc(6 × 2). On all three surfaces adsorption at 80 K yields surface potential changes in excess of 0.6 V and does not lead to the formation of an ordered overlayer. At high coverages the adsorption enthalpy is lower than on the clean surfaces. Infrared spectra show the growth of a doublet band with components initially at 2100 and 2117 cm^?1 on the oxidised Cu(111) surface. Similar features seen on the oxidised Cu(110) surfaces are accompanied by a band at 2140 cm^?1: a very weak band at the same frequency on oxidised Cu(111) is attributed to defect sites. Studies of the temperature dependence of the spectrum from oxidised Cu(111) lead to the conclusion that two different binding sites are occupied. Spectra of ${}^{12}\text{CO}{}^{13}\text{CO}$ mixtures show that the molecules occupying these sites are in close proximity to each other, and that the spectrum is subject to large but opposing coverage-dependent frequency shifts.     

Ultrathin Y2O3(111) films on Pt(111) substrates

The growth of ultrathin films of Y₂O₃(111) on Pt(111) has been studied using scanning tunneling microscopy (STM), X-ray photoemission spectroscopy (XPS), and low energy electron diffraction (LEED). The films were grown by physical vapor deposition of yttrium in a 10^? 6 Torr oxygen atmosphere. Continuous Y₂O₃(111) films were obtained by post-growth annealing at 700 °C. LEED and STM indicate an ordered film with a bulk-truncated Y₂O₃(111)–1 × 1 structure exposed. Furthermore, despite the lattices of the substrate and the oxide film being incommensurate, the two lattices exhibit a strict in-plane orientation relationship with the [11?0] directions of the two cubic lattices aligning parallel to each other. XPS measurements suggest hydroxyls to be easily formed at the Y₂O₃ surface at room temperature even under ultra high vacuum conditions. The hydrogen desorbs from the yttria surface above ~ 200 °C.     

Decompositional incommensurate growth of ferrocene molecules on a Au(111) surface

Deviating from the common growth mode of molecular films of organic molecules where the adsorbates remain intact, we observe an essentially different growth behavior for metallocenes with a low temperature scanning tunneling microscope. Ferrocene molecules adsorb dissociatively and form a two layer structure. The top layer unit cell is composed of two tilted cyclopentadienyl (cp) rings, while the first layer consists of ferrocene molecules and cp-Fe complexes. Surprisingly a fourfold symmetry is observed for the top layer while the first layer displays threefold symmetry elements. It is this symmetry mismatch which induces an incommensurability between these layers in all except one surface direction. The top layer is weakly bonded and has an antiferromagnetic ground state as calculated by local spin density functional approximation.     

Au(111)表面单个钴酞菁分子的去氢过程

利用低温超高真空扫描隧道显微镜对单个钴酞菁分子实现了选键化学反应.通过对吸附于Au(111)表面的单个钴酞菁分子外围H原子的"剪裁",并用实验图像和谱学方法,结合第一性原理理论计算研究了逐步去除钴酞菁分子8个外围H原子的过程.理论计算结果再现了实验中所观测到的分子空间构型的变化,并阐明了吸附体系中局域自旋的恢复和变化过程.     

States of water molecule adsorbed on Si(111) surface

Calculated electronic energy structure of an overlayer of water molecules chemisorbed on Si(111), with a molecular plane perpendicular to the surface, reveals that 3a₁ molecular state is removed upon adsorption, and the resulting state densities cannot be reconciled with the UPS spectrum. These results, and state densities obtained from different atomic configurations are interpreted to rule out the molecular adsorption on Si(111) surface at room temperature.     

Dissociation of water buried under ice on Pt(111)

Water on Pt(111) is generally thought to be nondissociative. However, by adsorbing a thick ice film [>150 monolayers (ML)], substantial (approximately 0.16 to 1 ML) dissociation of the "buried water" occurs for T>151 K. New temperature-programmed desorption peaks signal the dissociation (after careful isothermal predesorption of the overlying ice films). The buried water likely dissociates via the elevated temperatures and/or solvation changes experienced under the ice. Dissociation charges the growing ice film (up to +9 V) due to trapping of approximately 0.007 ML H3O+ at the vacuum-ice interface.