Interferometric two-photon photoemission correlation technique and femtosecond wet-electron dynamics at the TiO2 (110) surface

The femtosecond time-resolved two-photon photoemission (TR-2PP) and the ultra high vacuum (UHV) surface science techniques are integrated to investigate the electronic structures and the interfacial electron transfer dynamics at the atomically ordered adsorbate overlayers on TiO₂ singlecrystalline surfaces. Our research into the CH₃OH/TiO₂ system exhibits complex dynamics, providing abundant information with regard to electron transport and solvation processes in the interfacial solvent structures. These represent the fundamentally physical, photochemical, and photocatalytic reactions of protic chemicals covered with metal-oxides.      

Interferometric two-photon photoemission correlation technique and femtosecond wet-electron dynamics at the TiO (110) surface

The femtosecond time-resolved two-photon photoemission (TR-2PP) and the ultra high vacuum (UHV) surface science techniques are integrated to investigate the elec- tronic structures and the interfacial electron transfer dynamics at the atomically ordered adsorbate overlayers on TiO₂ single- crystalline surfaces. Our research into the CH₃OH/TiO₂ system exhibits complex dynamics, providing abundant informa- tion with regard to electron transport and solvation processes in the interfacial solvent structures. These represent the fundamentally physical, photochemical, and photocatalytic reactions of protic chemicals covered with metal-oxides.     

利用飞秒双光子光电子发射研究GaAs(100)的自旋动力学过程

超短激光技术的发展为研究材料中的超快光动方学过程提供了重要的实验手段，也使得人们 能够更为深入地研究电子的自旋动力学行为.GaAs(100)表面由于费米钉扎而会导致能带弯曲 ，位于该区域的电子及其自旋特性将会明显不同于体相材料中的情况.利用时间分辨和自旋 分辨的双光子光电子发射技术研究了p型掺杂GaAs(100)表面的电子极化动力学过程.结果表 明，由费米钉扎而引起的能带弯曲明显影响电子的自旋弛豫过程，从实验上观察到了GaAs(1 00)表面能带弯曲区域的电子自旋翻转时间存在近2个量级的差异(从几纳秒到几十皮秒)，基 于电子-自旋交换相互作用的BAP机理在自旋弛豫过程中起着主导作用. 关键词： 光物理 自旋极化 双光子光电子发射 砷化镓     

Intrinsic nature of the excess electron distribution at the TiO2(110) surface

The gap state that appears upon reduction of TiO2 plays a key role in many of titania's interesting properties but its origin and spatial localization have remained unclear. In the present work, the TiO2(110) surface is reduced in a chemically controlled way by sodium adsorption. By means of resonant photoelectron diffraction, excess electrons are shown to be distributed mainly on subsurface Ti sites strikingly similar to the defective TiO2(110) surface, while any significant contribution from interstitial Ti ions is discarded. In agreement with first principles calculations, these findings demonstrate that the distribution of the band gap charge is an intrinsic property of TiO2(110), independent of the way excess electrons are produced.     

Role of bulk thermal defects in the reconstruction dynamics of the TiO2(110) surface

We use low-energy electron microscopy to show that changing the temperature of oxygen-deficient, rutile-structure crystals causes steps on the (110) surfaces to move. This motion occurs because the concentration of bulk oxygen vacancies changes with temperature, requiring that material be added to or subtracted from the surface. During cooling below a bulk-stoichiometry-dependent temperature, the surface reconstructs into a 1x2 structure in the regions surface steps have swept through, showing that the structural and compositional changes needed to form the 1x2 phase are facilitated by the surface-to-bulk mass flow.     

Defect states at the TiO2(110) surface probed by resonant photoelectron diffraction

The charge distribution of the defect states at the reduced TiO(2)(110) surface is studied via a new method, the resonant photoelectron diffraction. The diffraction pattern from the defect state, excited at the Ti-2p-3d resonance, is analyzed in the forward scattering approach and on the basis of multiple scattering calculations. The defect charge is found to be shared by several surface and subsurface Ti sites with the dominant contribution on a specific subsurface site in agreement with density functional theory calculations.     

Stability of gold nanostructures on rutile TiO2(110) surface

The adsorption of gold atoms and formation of nanostructures on the rutile TiO₂(110) surface with different degree of oxygen reduction was studied from first principles. The Au atoms adsorb strongest at oxygen vacancy sites. Starting from a very low coverage limit the potential energy profiles or diffusion paths of the adsorbed Au monomers and dimers were calculated. Stable structures of two to nine Au atoms arranged in finite and infinite rows and in the shape of finite-size clusters were determined. All these structures are found to bind to the reduced surface stronger than 2 eV/atom. The elongated Au row-like structures bind by about 0.1 eV stronger than 3D clusters, suggesting a preference for the 1D-like Au growth mode on the missing-row reconstructed TiO₂(110).     

First-principles molecular dynamics simulations of uranyl ion interaction at the water/rutile TiO2(110) interface

The effects of temperature and solvation on uranyl ion adsorption at the water/rutile TiO₂(110) interface are investigated by Density Functional Theory (DFT) in both static and Born–Oppenheimer molecular dynamics approaches. According to experimental observations, uranyl ion can form two surface complexes in a pH range from 1.5 to 4.5. Based on these observations, the structures of the complexes at 293 K are first calculated in agreement with vacuum static calculations. Then, an increase in temperature (293 to 425 K) induces the reinforcement of uranyl ion adsorption due to the release of water molecules from the solvation shell of uranyl ion. Finally, temperature can modify the nature of the surface species.     

Pyrocatechol as a surface capping molecule on rutile TiO2 (110)

A ‘cap and dip’ method of adsorbing ruthenium di-2,2′-bipyridyl-4,4′-dicarboxylic acid diisocyanate (N3 dye) on a rutile TiO₂ (110) surface was investigated using pyrocatechol as a capping molecule. This method involves cleaning the rutile surface in ultra-high vacuum (UHV), depositing pyrocatechol onto the surface to ‘cap’ the adsorption sites, removing from vacuum, ‘dipping’ in an N3 dye solution and returning to vacuum. Photoemission measurements following the return of the crystal to vacuum suggest that the pyrocatechol keeps the surface free from contamination on exposure to atmosphere. Photoemission spectra also indicate that the pyrocatechol capping molecules are replaced by the N3 dye in solution and that the N3 dye is adsorbed intact on the rutile TiO₂ (110) surface. This technique may allow other large molecules, which are thermally unstable to evaporation in UHV, to be easily deposited onto TiO₂ surfaces.     

Dynamical and structural properties of adsorbed water molecules at the TiO2 rutile-(110) surface: interfacial hydrogen bonding probed by ab-initio molecular dynamics

ABSTRACT

Ab-initio molecular dynamics (AIMD) simulations have been carried out to study a range of different and energetically-accessible adsorbed-water configurations and motifs for their vibrational and structural characteristics, in contact with rutile-(110) interfaces at 100?K. The radial pair distribution function between the titanium atoms at the interface and the hydrogen and oxygen atoms in the water monolayer show an orientation of the water molecules parallel to the surface of titania, and with hydrogen atoms pointed in the opposite direction to the surface. In some cases, a distinctive vibrational frequency region between 2500 and 3000?cm^?1 has also been observed, due to a strong dispersion interaction between water molecules. This behaviour is also seen in experimental studies of thin-film water coverage on TiO₂ surfaces.     

Phonons at the Fe(110) surface

The in-plane density of phonon states of clean Fe(110) surface was measured separately for the first, second, and further atomic monolayers using nuclear inelastic scattering of synchrotron radiation. The results show that atoms of the first layer vibrate with frequencies significantly lower and amplitudes much larger than those in the bulk, and that vibrational spectra along two perpendicular in-surface directions are different. The vibrations of the second layer are already very close to those of the bulk. The good agreement of the experimental results and the first-principles calculations allows for detailed understanding of the observed phenomena.     

Photoelectron diffraction study on the structure of a vanadium ultrathin film deposited at the TiO2(110) surface

This Letter reports an X-ray photoelectron diffraction study of ∼5 V monolayers deposited by electron beam evaporation at the TiO₂(110) surface. Data clearly show that V grows as islands with a bcc structure having the [100] direction normal to the substrate surface. A detailed analysis of the V″2p and Ti″3p azimuthal curves indicates also an alignment of the [001] overlayer azimuth with the [1¯10] direction of the TiO₂ substrate. These results are consistent with an epitaxial growth of bcc V at the TiO₂(110) surface where a double V surface unit cell is matched to the TiO₂(110) rectangular cell.     

Titanium overlayers on TiO2(110)

Non-stoichiometric, Ti-rich TiO₂(110) surfaces were prepared by evaporation of Ti on stoichiometric TiO₂(110). Changes in the spectra of core levels, valence bands, Auger emissions, electron energy losses, conductivities and work functions were investigated during overlayer formation in the monolayer range and during subsequent annealing of non-stoichiometric surfaces at high temperatures and high oxygen partial pressures. These annealing procedures make it possible to restore the ideal stoichiometry of TiO₂(110). The results are discussed quantitatively by calculating concentrations of (sub)surface intrinsic defects in a space-charge layer model.