Charge localization dynamics induced by oxygen vacancies on the TiO₂(110) surface

The dynamics of an F center created by an oxygen vacancy on the TiO?(110) rutile surface has been investigated using ab initio molecular dynamics. These simulations uncover a truly complex, time-dependent behavior of fluctuating electron localization topologies in the vicinity of the oxygen vacancy. Although the two excess electrons are found to populate preferentially the second subsurface layer, they occasionally visit surface sites and also the third subsurface layer. This dynamical behavior of the excess charge explains hitherto conflicting interpretations of both theoretical findings and experimental data.     

STM investigation of the reaction of AgO added rows with CO2 on a Ag(110) surface

The formation of carbonate species by a reaction of AgO added rows with CO₂ was investigated by scanning tunneling microscopy (STM). STM observation during the reaction revealed that the AgO added rows were compressed from a (4 × 1) to a (2 × 1) phase, according to the growth of carbonate domains. Though the carbonate domains give a (1 × 2) diffraction pattern, STM images of this domain do not show a (1 × 2) structure, which indicates that the Ag substrate reconstructs to a (1 × 2) structure. Though the CO₃ species thermally decompose at a lower temperature than AgO added rows, the AgO added rows can be selectively decomposed by ultraviolet irradiation.     

Enhanced atomic-scale contrast on Fe3O4 (100) observed with an Fe STM tip

Clean (100) surfaces of a synthetic single crystal of magnetite (Fe₃O₄) have been prepared in situ using current pulses in a scanning tunneling microscope without subsequent annealing. We have observed atomically resolved terraces with rows of Fe²⁺ and Fe³⁺ ions of the B-sublattice (octahedrally coordinated lattice sites). Along these rows a long-distance corrugation (∼12 ?) has been observed at 300 K using in situ prepared Fe tunneling tips. This corrugation is interpreted as a Wigner localization associated with a Verwey transition above 300 K in the top surface layer. Received: 26 September 2000 / Accepted: 27 October 2000 / Published online: 3 May 2001     

金红石型TiO2(110)表面性质及STM形貌模拟

采用密度泛函理论从头计算了金红石型TiO2(110)表面的相关性质,切片模型含有9层原子,采用化学整比表面结构,晶胞真空层厚度为1.5nm,原子价电子采用超软赝势表达.差分电子密度分布图发现原子附近区域电子密度分布以球对称为主,电子定域形成离子键的趋势较强,但在Ti和O原子之间存在较弱的共价键.模拟了金红石型TiO2(110)表面结构的扫描隧道显微镜(scanning tunneling microscope,简称STM)图像,利用Tersoff-Hamann的成像理论,在 2 V的正向偏压下,采用一系列变化的数值作为STM探针离表面桥式氧的距离,分析了相关态密度的变化,发现(110)表面的STM形貌凸起部分来自于5-Ti原子,而不是2-O原子(桥式氧),在TiO2(110)表面结构成像中,电子效应起主导作用,证实了STM实验观察到的亮行是Ti原子的结果.     

STM study of the Ni(110)-(2 × 1)-2CO system: structure and bonding-site determination

The structure of the Ni(110)-(2 × 1)-2CO system has been studied with scanning tunneling microscopy (STM) at room temperature. Contrary to many previous studies, it is found that atomically-resolved STM imaging of CO molecules is attainable. By comparing the apparent CO adlayer registry with coadsorbed low concentrations of O and S, it is found that the CO molecules bond in short-bridge sites along the Ni [11̄0] rows and alternately tilt away from the normal direction within the (001) plane.     

Reflective Ability and Radiation Stability of BaZrxTi(1–x)O3 Powders Synthesized with the Use of TiO2 Nanoparticles

Russian Physics Journal -     

Numerical investigation of the submonolayer growth and relaxation of stepped Ag (110) and Au (110) surfaces

The terrace width distribution (TWD) as well as the adatom and island densities for some stepped fcc?(110) surfaces with parallel and equidistant steps of equal stiffness are studied by means of kinetic Monte Carlo simulations. Reliable energy barriers for surface diffusion are used. They have been calculated by means of many-body potentials derived within the second moment approximation to the tight-binding model. The effects of the temperature, atom deposition flux and surface diffusion on quantities of interest in the early stage of the surface evolution process have been singled out. In most cases, linear, logarithmic and power-law behaviors are recovered for the evolution of the step width and terrace defects. The TWD is well described by the Gaussian distribution (GD) in the domain of temperature investigated but deviates from the Generalized Wigner Distribution (GWD).     

Geometric and electronic structure of epitaxial NbxTi1−xO2 on TiO2(110)

We have investigated the detailed geometric and electronic structure of MBE-grown Nb_xTi_1−xO₂ on TiO₂(110) by means of high-resolution transmission electron microscopy, X-ray photoelectron diffraction, ultraviolet and X-ray photoemission and electron energy loss spectroscopy. We find no measurable change in the NbO bond length relative to that for TiO bonds in TiO₂ in the dilute limit (x = 0.05), and that the epitaxial layers remain strained and coherent with the substrate for x ⩽ ≈ 0.3. However, significant dislocation generation occurs for x > ≈ 0.3. Nb substitution for Ti in the lattice introduces an additional valence electron per atom. The resulting density of states falls in the valence band region, but no new state density occurs in the either the band gap or conduction band. This result is in contrast to what occurs in the very dilute limit (parts per thousand), where Nb electrons occupy a shallow donor level near the conduction band minimum. Based on the electron counting rule, the extra Nb electrons form a non-bonding band which is degenerate with the valence band. The significance of these results for enhanced thermal and photochemistry on Nb_xTi_1−xO₂ surfaces vis a vis TiO₂ is discussed.     

A Comparative Study of the Growth of Cr on (110)TiO2 Rutile, (0001) α-Al2O3 and (100)SrTiO3 Surfaces

Thin Cr films were deposited on single crystal -Al₂O₃, SrTiO₃ and TiO₂ (rutile) substrates under ultrahigh vacuum conditions using molecular beam epitaxy (MBE). The growth behavior and thermal stability of the films were investigated with scanning tunneling microscopy (STM), X-ray phototelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and transmission electron microscopy (TEM). Cr grew as 3D clusters on all substrates. For all three Cr/oxide systems a strong temperature dependent interfacial reaction was observed. The results suggested that these reactions depended greatly on thermodynamics and on transport properties in the oxide substrates.     

Dispersion of the oxygen-induced bands on Cu (110) - an angle-resolved ups study of the system p(2×1)O/Cu(110)

The two-dimensional electronic energy bands induced by adsorption of atomic oxygen on Cu(110) are measured with angle-resolved photoelectron spectroscopy (ARUPS). Three oxygen-derived bonding bands and two Cu - derived antibonding bands are found below the Fermi energy. The dispersions can be described by assuming nearest-neighbour σ and π CuO bonds along the [001] direction with oxygen in a long bridge site.     

Observation of Phase Transitions in an Electron–Hole System Associated with Dislocation Cores in Cadmium Telluride

Bulletin of the Lebedev Physics Institute - Evolution of the fine structure of dislocation microphotoluminescence lines in cadmium telluride with a decrease in the optical-excitation power density...     

DFT study of isocyanate chemisorption on Cu(100): Correlation between substrate–adsorbate charge transfer and intermolecular interactions

The adsorption of isocyanate (? NCO) species on Cu(100) was studied using the density functional theory (DFT) and the periodic slab model. The calculations indicate that at low and intermediate coverages NCO adsorbs preferentially on bridge and hollow sites. Work function and dipole moment changes show a significant negative charge transfer from Cu to NCO. The resulting charged NCO species interact repulsively among themselves being these dipole–dipole interactions particularly intensive when they are adsorbed in adjacent sites. Consequently, isocyanates tend to be separated from each other generating the vacant sites required for the dissociation to N and CO. This condition for NCO dissociation has been suggested in the past from experimental observations. A comparison was also performed with the NCO adsorption on Pd(100). In particular, the calculated minimal energy barrier for NCO dissociation was found to be higher on Cu(100) than on Pd(100) in accord with the well known higher NCO stability on Cu(100).     

Characterization of Rh,Mo and Rh–Mo particles formed on TiO2(110) surface: A TDS,AES and RAIRS study

The structural and chemical characterization of Rh, Mo and Rh–Mo nanosized clusters formed by physical vapor deposition on TiO₂ single crystal was performed by Auger Electron Spectroscopy (AES), Thermal Desorption Spectroscopy (TDS) and Reflection Absorption Infrared Spectroscopy (RAIRS), applying CO as test molecule. On a slightly reduced titania surface 2D-like growth of Rh was revealed at 300 K up to 0.23 ML coverage by AES and CO-desorption experiments. For CO-saturated Rh particles TDS showed molecular CO desorption in a broad temperature range with T_p = 400, 440, 490 and 540 K (α-states), the latter state appearing only on the smallest Rh particles. The population of γ-state (T_p = 780–820 K) originating from the recombination of C and O atoms on the support began at Θ_Rh = 0.23ML and was maximized at around 1–2 ML Rh coverage, corresponding to 30% dissociation of CO. A possible dissociation precursor on Rh particles is identified as linearly bonded CO on step sites characterized by ν(C–O) of 2017 cm^? 1. Deliberation of CO₂ could not be detected between 170 and 900 K, showing the absence of disproportionation reaction. Instead of oxidizing CO molecules, oxygen atoms stemming from the dissociation of CO attached to the reduced centers of titania, indicating the role of adsorption sites at the perimeter of Rh particles in the decomposition process. 2 ML of predeposited Mo enhanced markedly the dispersion of Rh particles as a result of strong Rh–Mo interaction, but it slightly reduced the molecular α-CO desorption possibly due to enhanced dissociation. The formation of γ-CO was suppressed considerably through elimination of adsorption centers by Mo on the TiO₂ substrate. The reactivity of Rh layers deposited on Mo-covered surface towards CO was reduced after repeated annealing to 600 K due to partial encapsulation of Rh by titania, manifesting in the suppression of the more strongly bonded α-state. Mo-deposits (up to 0.5ML) on Rh particles decreased the saturation coverage of α-CO through a site-blocking mechanism without detectable influence on the binding energy of CO to Rh, indicating Mo island formation. The carbon arising from the decomposition of CO dissolved in the Mo-containing particles formed a solid solution stable even at 900 K, suggesting a possible role of molybdenum carbide regarding the enhanced catalytic activity of Rh clusters.     

STM study of Pd growth on TiO2(100)-(1 × 3)

STM has been used to study the initial growth of palladium on TiO₂(100)-(1 × 3). The results demonstrate that STM is capable of imaging individual atoms which form part of a supported metal cluster. The data were obtained from small (35Ådiameter by 8Åhigh) clusters at a dispersed-equivalent coverage of about 0.01 ML. At higher coverages the clusters coalesce.     

Co-adsorption of O_2 and H_2O on α-uranium(110) surface:A density functional theory study

First-principles calculations based on density functional theory corrected by Hubbard parameter U(DFT+U) are applied to the study on the co-adsorption of O2 and H_2O molecules to α-U(110) surface. The calculation results show that DFT+U method with Ueff= 1.5 e V can yield the experimental results of lattice constant and elastic modulus of α-uranium bulk well. Of all 7 low index surfaces of α-uranium, the(001) surface is the most stable with lowest surface energy while the(110) surface possesses the strongest activity with the highest surface energy. The adsorptions of O_2 and H_2O molecules are investigated separated. The O_2 dissociates spontaneously in all initial configurations. For the adsorption of H_2O molecule,both molecular and dissociative adsorptionsoccur. Through calculations of co-adsorption, it can be confirmed that the inhibition effect of O_2 on the corrosion of uranium by water vapor originates from the preferential adsorption mechanism,while the consumption of H atoms by O atoms exerted little influence on the corrosion of uranium.     

Superhalogen properties of ReOn (n = 1–5) species and their interactions with an alkali metal: an ab initio study

First principle density functional approach is employed to investigate the ground-state geometries and stabilities of ReO_n species (n = 1–5) in neutral as well as anionic forms. It is revealed that Re can bind stably with five O atoms indicating the maximum oxidation state of Re as high as +10. The electron affinities of ReO_n suggest that these species behave as superhalogens for n ≥ 3 which become as large as 7.25 eV for n = 5. The interaction of ReO_n superhalogens with appropriate alkali metals is stronger than that of halogens leading to the synthesis of more stable complex compounds. This idea is illustrated by considering the interaction of ReO_n superhalogens with K atom, forming KReO_n complexes which are relatively more stable than KF molecule. In such complexes, ReO_n unit closely mimics the behaviour of F atom when compared with KF.     

Growth of CuO chains on Ag(110) surfaces

The (AgO) chains grown along the 〈001〉 direction on Ag(110) disappeared by the reaction with Cu atoms at room temperature, and new one-dimensional chains grew in the 〈110〉 direction. The STM images at different bias potentials suggest the growth of (CuO) chains in the 〈110〉 direction on the Ag(110) surface. The (CuO) chains on the Ag(110) surface disappeared by heating to 470 K, but they reappeared by exposing to O₂ at room temperature.