Adsorption of L-cysteine on rutile TiO2(110)

We have used X-ray photoelectron spectroscopy to study the adsorption of L-cysteine on a rutile TiO₂(110) surface at room temperature and ? 65 °C. For the molecules in direct contact with the surface our results suggest that the molecules bind dissociatively to the fivefold-coordinated Ti atoms of the surface through their deprotonated carboxylic groups. A second, dissociative interaction occurs between the molecular thiol groups and the surface. It is attributed to a dissociative bond to the bridging oxygen vacancies. Most likely, the thiol groups are deprotonated and a bond is formed between the thiolates and defects. In an alternative scenario, the C–S bond is cleaved and atomic sulfur binds to the defects. With regard to the molecular amino groups, they remain neutral at the lowest investigated coverages (0.3–0.5 ML), but already starting from around 0.7 ML nominal coverage protons are being transferred to them. The fraction of protonated amino groups increases with coverage and becomes dominating in multilayers prepared at room temperature and ? 65 °C. In these multilayers the carboxylic groups are deprotonated.     

Methylene bromide chemistry and photochemistry on rutile TiO2(110)

The chemistry and photochemistry of methylene bromide (CD₂Br₂) on the rutile TiO₂(110) surface was probed using temperature programmed desorption (TPD). CD₂Br₂ desorbed in three desorption states at 145, 160 and 250 K tentatively assigned to desorption from the multilayer, from an η¹-CD₂Br₂ species and a bridging η²-CD₂Br₂ species, respectively. The latter two TPD states presumably involve binding of CD₂Br₂ molecules to the surface through Br coordination at five-coordinate Ti⁴⁺ surface sites. The 160 and 250 K TPD states saturated at coverages of 1.0 and 0.33 ML, respectively, where 1 ML is equivalent to the surface Ti⁴⁺ site density (5.2 × 10¹⁴ cm^? 2). No thermal decomposition of CD₂Br₂ was observed on either the clean surface or with preadsorbed O₂. UV irradiation of CD₂Br₂ on TiO₂(110) resulted in predominately photodesorption, with trace amounts of photodecomposition evidenced in TPD. The rate of CD₂Br₂ photodesorption from TiO₂(110) occurred with a low cross section (~ 2 × 10^? 21 cm²) similar to that expected from direct optical excitation of CD₂Br₂. This observation suggests that charge carriers generated in TiO₂(110) were no more effective in activating adsorbed CD₂Br₂ molecules than would be expected through direct molecular excitation. These findings suggest that photocatalytic destruction of halocarbons such as CD₂Br₂ on TiO₂ may preferentially occur though indirect processes (such as OH radical attack) as opposed to direct electron transfer processes involving charge carriers generated in TiO₂ by bandgap excitation.     

Vacancy-assisted diffusion of alkoxy species on rutile TiO2(110)

Using scanning tunneling microscopy (STM) and density functional theory simulations, we have studied the diffusion of alkoxy species formed by the dissociation of alcohols on bridge-bonded oxygen (BBO) vacancies (BBO(V)'s) on TiO2(110). At elevated temperatures (>or=400 K) the sequential isothermal STM images show that mobile BBO(V)'s mediate the diffusion of alkoxy species by providing space for alkyl-group-bearing BBO atom to diffuse into. The experimental findings are further supported by simulations that find that BBO(V) diffusion is the rate limiting step in the overall diffusion mechanism.     

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).     

Direct evidence for ethanol dissociation on rutile TiO2(110)

We have studied the interaction of ethanol with reduced TiO(2)(110)-(1 × 1) by high-resolution scanning tunneling microscopy (STM) measurements and density functional theory calculations. The STM data revealed direct evidence for the coexistence of molecularly and dissociatively adsorbed ethanol species on surface Ti sites. In addition, we found evidence for dissociation of ethanol at bridge-bonded O vacancies. The density functional theory calculations support these findings and rationalize the distinct diffusion behaviors of molecularly and dissociatively adsorbed ethanol species, as revealed in time-lapsed STM images.     

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.     

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO2(110) system involving vacancy-cluster complex diffusion is presented.     

Interplay between external strain and oxygen vacancies on a rutile TiO2(110) Surface

Comprehensive first-principle calculations on strained rutile TiO2(110) indicate that the formation energy of different types of oxygen vacancies depends on the external strain. For the unstrained state, the energetically favorable oxygen vacancy (EFOV) appears on the bridging site of the first layer; when 3% tensile strain along [11[over ]0] is applied, EFOV moves to the in-plane site, while 2% compressive strain along either [001] or [11[over ]0] shifts EFOV to the subbridging site. We therefore suggest that the distribution of oxygen vacancies can be engineered by external strain, which may help to improve the applications of a TiO2 surface where oxygen vacancy plays an important role.     

第一性原理计算C掺杂金红石型TiO2的磁性和光学性质

本文运用第一性原理GGA+U方法计算了C元素单/双掺杂金红石型TiO2的电子结构、磁性和光学性质. 结果表明, C掺杂体系的晶格发生畸变和体积相应增大。单掺杂体系的磁矩为1.3 μB, 磁矩主要归因于杂质态引起的自旋电荷密度不平衡, 杂质态主要由C-2p、O-2p 和Ti-3d的态电子构成, 且它们之间存在明显的杂化现象. 双掺杂体系中C原子之间的反铁磁性耦合比铁磁性耦合更加稳定, 但其磁矩为零. 另外, 随着掺杂浓度的增大, 掺杂体系的带隙由2.58 eV增大到3.4 eV, 且在可见光区域的光吸收效率明显增大. 这表明带隙的减小可能不是光谱吸收增强的主要因素, 而带隙中的杂质态极大地影响了光谱吸收效率.     

第一性原理计算C掺杂金红石型TiO_2的磁性和光学性质

本文运用第一性原理GGA+U方法计算了C元素单/双掺杂金红石型TiO_2的电子结构、磁性和光学性质.结果表明,C掺杂体系的晶格发生畸变和体积相应增大.单掺杂体系的磁矩为1.3μB,磁矩主要归因于杂质态引起的自旋电荷密度不平衡,杂质态主要由C-2p、O-2p和Ti-3d的态电子构成,且它们之间存在明显的杂化现象.双掺杂体系中C原子之间的反铁磁性耦合比铁磁性耦合更加稳定,但其磁矩为零.另外,随着掺杂浓度的增大,掺杂体系的带隙由2.58 eV增大到3.4 eV,且在可见光区域的光吸收效率明显增大.这表明带隙的减小可能不是光谱吸收增强的主要因素,而带隙中的杂质态极大地影响了光谱吸收效率.     

TiO2纳米层(110)表面对DNA强吸附的第一性原理研究

纳米二氧化钛(TiO₂)由于具有卓越的生物相容性和优异的物理性能,因此有望在生物医学领域中发挥重要的作用,且应用前景广阔.利用第一性原理计算,深入地研究了金红石型TiO₂纳米层(110)表面与脱氧核糖核酸(DNA)不同碱基在界面之间的吸附性能及相互作用的原子机制.通过分析结合能和功函数的计算结果发现,TiO₂纳米层(110)表面对DNA碱基的吸附强度显著增强,比典型二维纳米材料的吸附强度大两倍以上.进而,通过研究电子能带结构和态密度计算结果,阐明了二者在界面之间的吸附机制,其起源于吸附体系显著降低的能级和C、N和/或O的2p轨道与费米能级附近Ti原子的3d轨道的强烈杂化.纳米TiO₂为DNA传感器和测序仪的设计提供了一种极具潜力的候选材料.     

Pressure and temperature dependences of the elastic properties of rutile (TiO2)

Using ultrasonic techniques we have measured the pressure and temperature dependences of the six elastic constants of single-crystalline rutile (TiO₂). The pressure measurements were made in the range 0–20 kbar at room temperature, and the temperature measurements were made in the range 80–300°K at atmospheric pressure. Our results are in good agreement with the results recently reported by Manghnani et al., although our pressure derivatives are generally a few per cent smaller than theirs and our temperature derivatives a few per cent more negative (at 298°K). Nonlinear pressure dependences were observed for some of the elastic constants. A relation between the pressure-induced softening of two lattice modes (one optic and one acoustic) and a possible pressure-induced transition to the CaCl₂ structure is discussed. An approximate separation of the isobaric temperature derivatives of the elastic constants into “pure” volume and temperature contributions is considered. In particular, an attempt is made to estimate the magnitude of the error made in effecting this separation using equations applicable to cubic rather than tetragonal symmetry. It is shown that, in principle, these errors could be significant.     

First-principles study on electronic,magnetic properties and optical absorption of vanadium doped rutile TiO2

The electronic, magnetic properties and optical absorption of vanadium (V) doped rutile TiO₂ have been studied by the generalized gradient approximation GGA and GGA+U (Hubbard coefficient) approach respectively. On the one hand, we consider the influence of vanadium with different doping concentration on the electronic structure. On the other hand, we study double V atoms doped TiO₂, mainly study four V-doped TiO₂ configurations, and find the magnetic ground states are ferromagnetic state. For the TiO₂@V-V1, TiO₂@V-V3 and TiO₂@V-V4 configurations without O ion as bridge between V-V atoms, there will have a metastable state of antiferromagnetic configurations, while, for the TiO₂@V-V2 configurations with an O ion as bridge between V-V atoms, due to the existence of superexchange between V-O-V, there will only exist the ground state of ferromagnetic state and there are no other metastable configurations. Furthermore, the optical properties of V-doped TiO₂ are calculated. The results show that the V-doped TiO₂ has strong infrared light absorption and visible light absorption.     

Molecular chemisorption as the theoretically preferred pathway for water adsorption on ideal rutile TiO2(110)

By taking careful account of slab thickness and adsorbate orientation effects we present, for the first time, periodic density functional calculations predicting the preference of water to adsorb in a molecular state on the ideal rutile TiO2(110) surface at all coverages < or =1 monolayer (ML). Moreover, while this has been predicted previously for 1/4 ML coverage [Phys. Rev. Lett. 87, 266104 (2001)]], we show that the assertion made in that work, that dissociation is energetically unfeasible on the ideal surface, is incorrect. Our results thus resolve a long-standing discrepancy between theory and experiment and significantly improve the understanding of water chemistry on TiO2 surfaces.     

Effect of Cr implantation on structural and optical properties of AlN thin films

Molecular beam epitaxy (MBE) grown AlN thin layer on sapphire substrates have been implanted with Cr⁺ ions for various dose from 10¹³ to 10¹⁵ cm⁻². The analyses were carried out by an X-ray diffractometer (XRD), Raman spectroscopy, a spectrophotometer and spectroscopic ellipsometry (SE) for structural and optical analyses. E₂(high) and A₁(LO) Raman modes of AlN layer have been observed and analyzed. The behavior of Raman shift and the variation in intensity and in peak width of Raman modes as a function of ions flux are explained on the basis of chromium substituting aluminum atom and implantation-induced lattice damage. Both Raman and X-ray analyses reveal that the incorporation of chromium atoms increases in the host lattice with the increasing of Cr ions fluence. The band gap energy was determined by using transmission spectra. It was found that the band gap energy decreases as the ion dose increases. The band gap of the unimplanted AlN is 6.02 eV and it decreases down to 5.92 eV for the Cr⁺-implanted AlN with a ion dose of 1×10¹⁵ cm⁻². Optical properties such as optical constants of the samples were examined by using a spectroscopic ellipsometer. It was observed that the refractive index (n) decreases with the increasing of ion dose.     

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.