Hydrogen bonding, H-D exchange, and molecular mobility in thin water films on TiO2(110)

Hydrogen bonding, H-D exchange, and molecular mixing in water films on TiO2(110) have been studied using water electron-stimulated desorption. For T<70 K, films with different water isotopes adsorbed on the Ti4+ and bridging oxygen rows can be prepared. For T>70 K, H-D and molecular exchange between these "layers" occur with a distribution of activation energies and is surprisingly efficient. The results demonstrate that all the water molecules that are directly bound to TiO2(110) -- i.e., in the first and second monolayers -- are also hydrogen bonded to each other.     

Site-dependent electron-stimulated reactions in water films on TiO2(110)

Electron-stimulated reactions in thin [<3 ML (monolayer)] water films adsorbed on TiO(2)(110) are investigated. Irradiation with 100 eV electrons results in electron-stimulated dissociation and electron-stimulated desorption (ESD) of adsorbed water molecules. The molecular water ESD yield increases linearly with water coverage theta for 0< or =theta< or =1 ML and 11 ML, the water ESD yield per additional water molecule adsorbed (i.e., the slope of the ESD yield versus coverage) is 3.5 times larger than for theta<1 ML. In contrast, the number of water molecules dissociated per incident electron increases linearly for theta< or =2 ML without changing slope at theta=1 ML. The total electron-stimulated sputtering rate, as measured by postirradiation temperature programmed desorption of the remaining water, is larger for theta>1 ML due to the increased water ESD for those coverages. The water ESD yields versus electron energy (for 5-50 eV) are qualitatively similar for 1, 2, and 40 ML water films. In each case, the observed ESD threshold is at approximately 10 eV and the yield increases monotonically with increasing electron energy. The results indicate that excitations in the adsorbed water layer are primarily responsible for the ESD in thin water films on TiO(2)(110). Experiments on "isotopically layered" films with D(2)O adsorbed on the Ti(4+) sites (D(2)O(Ti)) and H(2)O adsorbed on the bridging oxygen atoms (H(2)O(BBO)) demonstrate that increasing the water coverage above 1 ML rapidly suppresses the electron-stimulated desorption of D(2)O(Ti) and D atoms, despite the fact that the total water ESD and atomic hydrogen ESD yields increase with increasing coverage. The coverage dependence of the electron-stimulated reactions is probably related to the different bonding geometries for H(2)O(Ti) and H(2)O(BBO) and its influence on the desorption probability of the reaction products.     

Crystalline ice growth on Pt(111) and Pd(111): nonwetting growth on a hydrophobic water monolayer

The growth of crystalline ice films on Pt(111) and Pd(111) is investigated using temperature programed desorption of the water films and of rare gases adsorbed on the water films. The water monolayer wets both Pt(111) and Pd(111) at all temperatures investigated [e.g., 20-155 K for Pt(111)]. However, crystalline ice films grown at higher temperatures (e.g., T>135 K) do not wet the monolayer. Similar results are obtained for crystalline ice films of D2O and H2O. Amorphous water films, which initially wet the surface, crystallize and dewet, exposing the water monolayer when they are annealed at higher temperatures. Thinner films crystallize and dewet at lower temperatures than thicker films. For samples sputtered with energetic Xe atoms to prepare ice crystallites surrounded by bare Pt(111), subsequent annealing of the films causes water molecules to diffuse off the ice crystallites to reform the water monolayer. A simple model suggests that, for crystalline films grown at high temperatures, the ice crystallites are initially widely separated with typical distances between crystallites of approximately 14 nm or more. The experimental results are consistent with recent theory and experiments suggesting that the molecules in the water monolayer form a surface with no dangling OH bonds or lone pair electrons, giving rise to a hydrophobic water monolayer on both Pt(111) and Pd(111).     

Generation and Application of Ultra-High-Intensity Magnetic Field Gradient Pulses for NMR Spectroscopy

Two different concepts of gradient current power supplies are introduced, which are suitable for the generation of ultra-high intensity pulsed magnetic field gradients of alternating polarity. The first system consists of a directly binary coded current source (DBCCS). It yields current pulses of up to ±120 A and a maximum voltage across the gradient coil of ±400 V. The second system consists of two TECHRON 8606 power supplies in push–pull configuration (PSPPC). It yields current pulses of up to ±100 A and a maximum voltage across the gradient coil of ±300 V. In combination with actively shielded anti-Helmholtz gradient coils, both systems are used routinely in NMR diffusion studies with unipolar pulsed field gradients of up to 35 T/m. Until now, alternating pulsed field gradient experiments were successfully performed with gradient intensities of up to ±25 T/m (DBCCS) and ±35 T/m (PSPPC), respectively. Based on the observation of the NMR spin echo in the presence of a small read gradient, procedures to test the stability and the matching of such ultra-high pulsed field gradient intensities as well as an automated routine for the compensation of possible mismatches are introduced. The results of these procedures are reported for the PSPPC system.     

Wick Rotation for D-modules

We extend the classical Wick rotation to D-modules and higher codimensional submanifolds.     

Monte Carlo simulation studies of polymer systems

Polymers molecules in solution or melt are more or less flexible and continuously change their shape and size. Thus, characteristic properties of the system fluctuate around statistical mean values which are dependent on the concentration of the solution, on the quality of the solvent used, and on the specific structure of the molecules, e.g. linear or star-branched. The most direct approach to these quantities on a molecular level are computer simulations. Due to restrictions of computer power fully atomistic simulations of macromolecules are presently still at the beginning but several arguments justify the use of simplified models. The most efficient way dealing with polymer systems are Monte Carlo simulations based on lattice chains, at least as long as static properties are of interest only. In the present paper a short introduction to the field is given and selected examples are presented in order to demonstrate the usefulness of these methods.     

Design of titania porous films controlled by precursors’ viscosity for photocatalytic application

Research on Chemical Intermediates - Porous transparent films of TiO2 (anatase) were obtained by controlled hydrolysis of titanium tetraisopropoxide (sol-gel method) in the presence of a...     

Polynomials in operator space theory: matrix ordering and algebraic aspects

We extend the \(\lambda \)-theory of operator spaces given in Defant and Wiesner (J. Funct. Anal. 266(9): 5493–5525, 2014), that generalizes the notion of the projective, Haagerup and Schur tensor norm for operator spaces to matrix ordered spaces and Banach \(*\)-algebras. Given matrix regular operator spaces and operator systems, we introduce cones related to \(\lambda \) for the algebraic operator space tensor product that respect the matricial structure of matrix regular operator spaces and operator systems, respectively. The ideal structure of \(\lambda \)-tensor product of \(C^*\)-algebras has also been discussed.     

In-depth characterization and computational 3D reconstruction of flagellar filament protein layer structure based on in situ spectroscopic ellipsometry measurements

In this study, we have reconstructed the statistical 3D structure of hundreds of nanometers thick surface immobilized flagellar filament protein layers in their native environment, in buffer solution. The protein deposition onto the surface activated Ta₂O₅ film was performed in a flow cell, and the immobilization process was followed by in situ spectroscopic ellipsometry. A multilayer optical model was developed, in that the protein layer was described by five effective medium sublayers. Applying this method, an in-depth analysis of the protein layer formation was performed. Based on the kinetics in the distribution of the surface mass density, the statistical properties of the filamentous film could be determined computationally as a function of the measurement time. It was also demonstrated that the 3D structure of the protein layer can be reconstructed based on the calculated in-depth mass density profile. The computational investigation revealed that the filaments can be classified into two individual groups in approximately equal ratio according to their orientation. In the first group the filaments are close to laying position, whereas in the second group they are in a standing position, resulting in a significantly denser sublayer close to the substrate than at a larger distance.