Structure determination of the Cu(0 0 1)–c(4 × 4)-Sn surface by low-energy electron diffraction

Low-energy electron diffraction (LEED) have been used to determine the Cu(0 0 1)–c(4 × 4)-Sn structure formed at 300 K. It is demonstrated that a structural model suggested by scanning tunneling microscopy observations is correct: The model consists of one substitutional Sn atom and four Sn adatoms in the unit cell. Optimum parameters of the determined c(4 × 4) structure reveal that Sn adatoms laterally are displaced by 0.30 Å away from ideal fourfold-hollow sites along the 〈100〉 directions. It is proposed that such displacements of the Sn adatoms cause the formation of a network of octagonal rings on Cu(0 0 1). The substitutional Sn atom is located at each center of the octagonal rings. The formation conditions of the network are discussed.     

STM imaging of a model surface of Ru(4,4′-dicarboxy-2,2′-bipyridine)2(NCS)2 dye-sensitized TiO2 photoelectrodes

A TiO₂(1 1 0)-(1 × 1) surface was prepared in an ultra-high vacuum, transported in laboratory air, and observed with a scanning tunneling microscope (STM) operated in a vacuum of 10⁻⁴ Pa. Empty state images showed atomically flat terraces separated by single-height steps, on which 5-fold-coordinated surface Ti atoms were observed as spots arranged in a rectangular lattice. The Ru(4,4′-dicarboxy-2,2′-bipyridine)₂(NCS)₂ (N3) dye was adsorbed on the TiO₂ surface by immersing the TiO₂ wafer into an acetonitrile solution of the dye. In the empty state images, individual N3 molecules were observed as oval particles protruding by 0.6 nm from the TiO₂ surface. The oval shape elongated to the [1  0] directions was attributed to electron tunneling from tip to unoccupied states localized at the two carboxyl groups bound to the TiO₂ surface.     

Thermal stability of ZnO thin film prepared by RF-magnetron sputtering evaluated by thermal desorption spectroscopy

Thermal stability of sputter deposited ZnO thin films was evaluated by thermal desorption spectroscopy (TDS). Desorption of Zn was mainly observed from the films deposited at low O₂/Ar gas ratio and low RF power. In contrast, O₂ desorption was mainly observed from the films deposited at high O₂/Ar gas ratio and high RF power. The amount of desorbed O₂ from the film increased with increasing the O₂/Ar gas flow ratio and the RF power. Furthermore, the desorption temperature of O₂ increased with increasing the RF power during the deposition. Thermal stability of the ZnO films was controlled not only by the O₂/Ar gas flow ratio, but also applied RF power to the target.     

Nonlinear conjugate gradient methods with structured secant condition for nonlinear least squares problems

In this paper, we deal with conjugate gradient methods for solving nonlinear least squares problems. Several Newton-like methods have been studied for solving nonlinear least squares problems, which include the Gauss-Newton method, the Levenberg-Marquardt method and the structured quasi-Newton methods. On the other hand, conjugate gradient methods are appealing for general large-scale nonlinear optimization problems. By combining the structured secant condition and the idea of Dai and Liao (2001) [20], the present paper proposes conjugate gradient methods that make use of the structure of the Hessian of the objective function of nonlinear least squares problems. The proposed methods are shown to be globally convergent under some assumptions. Finally, some numerical results are given.     

Time-resolved infrared spectroscopy of K3Ta3B2O12 photocatalysts for water splitting

Electrons photoexcited in K(3)Ta(3)B(2)O(12), an efficient photocatalyst for the water-splitting reaction driven by ultraviolet light, were observed using time-resolved IR absorption spectroscopy with microsecond resolution. When the catalyst was irradiated with 266 nm light pulses, a structureless absorption appeared at 3000-1500 cm(-1). The absorption was assigned to the optical transition of electrons that were band gap-excited and then trapped in mid-gap states. The absorbance decayed with a time delay because of the electron-hole recombination. The rate of recombination in an argon atmosphere was sensitive to the composition of the starting material used in the catalyst preparation. The electron decay was accelerated by exposing the catalyst to water vapor. The degree of acceleration was qualitatively correlated with the H(2) production rate observed during steady-state light irradiation.     

Structural study of NO adsorbed on the reconstructed Pt(110)-(1 x 2) surface with X-ray photoelectron diffraction and near-edge X-ray absorption fine structure spectroscopy

The adsorption structure of NO on the reconstructed Pt(110)-(1 x 2) surface was studied with X-ray photoelectron spectroscopy (XPS), X-ray photoelectron diffraction (XPD), low-energy scanned-angle photoelectron diffraction (LESA-PD), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The experiments were performed at 180 K, where no surface lifting from (1 x 2) to (1 x 1) takes place after NO adsorption. XPS indicates that the (1 x 2) unit cell of the Pt(110) surface contains 1.5 NO molecules at the saturated coverage. XPD and LESA-PD analyses allow us to propose a structural model for the NO adlayer, where two-thirds of the NO molecules in the (1 x 2) unit cell are adsorbed on the atop site of the close-packed Pt rows (ridges) along the [10] direction with an inclined geometry and one-third of the NO molecules adsorb on the bridge site between the Pt ridges with an upright configuration. This model is supported by the N K-edge NEXAFS experiments and is consistent with the recently reported model based on the density functional theory (Orita, H.; Nakamura, I.; Fujitani, T. J. Phys. Chem. B 2005, 109, 10312).     

Synthesis of brominated directly fused diporphyrins through gold(III)-mediated oxidation

Highly efficient synthesis of meso,meso-dibromo doubly and triply fused diporphyrins has been achieved through a powerful oxidative coupling mediated by AuCl3-AgOTf combination. In addition, palladium-catalyzed debromination of meso-bromoporphyrins has been developed. This debromination protocol enables employment of bromine as a protecting group for the reactive meso-position of porphyrins.     

Synthesis and light-emitting properties of bipolar oligofluorenes containing triarylamine and 1,2,4-triazole moieties

A facile approach for synthesis of bipolar oligofluorenes, TAZ-OF(n)-NPh, n = 2 or 3 end-capped with hole-transporting diphenylamino and electron-transporting triazole moieties by Suzuki cross-coupling as the key reaction has been developed. This novel bipolar oligofluorenes exhibited blue-emission, high thermal and morphological stabilities. The single-layer OLED based on TAZ-OF(2)-NPh exhibited superior device performance with a maximum luminance of 1128 cd m(-2) and luminance efficiency of up to 0.83 cd A(-1).     

TiCl4 induced anti-Markovnikov rearrangement

Stereoisomeric bicyclic tert-alcohols afforded identical ring-expansion products via cationic anti-Markovnikov rearrangement from perpendicular tert-cations into identical six-membered ring secondary cations by the treatment with TiCl4. These results provide evidence that the reaction takes place by the cationic stepwise mechanism. [reaction: see text]