A coarse-graining approach for the proton complex in protonated aluminosilicates

We have developed a computational framework for the adsorption of linear alkanes in protonated aluminosilicates. These zeolites contain trace amounts of water that form hydrated proton complexes. The presence of hydrated protons makes the simulations at the fully atomistic level difficult. Instead of constructing an elaborate and complex model, we show that an approach based on a coarse-graining of the proton-complex accurately describes the available experimental isotherms, Henry coefficients, heats of adsorption, and oxygen-proton distances. Our approach is supported by MP2 quantum mechanical simulations. The model gives remarkably good agreement with experimental data beyond the initial calibration set.     

Influence of a TiCl4 post-treatment on nanocrystalline TiO2 films in dye-sensitized solar cells

In this study, the influence of the TiCl(4) post-treatment on nanocrystalline TiO(2) films as electrodes in dye-sensitized solar cells is investigated and compared to nontreated films. As a result of this post-treatment cell efficiencies are improved, due to higher photocurrents. On a microscopic scale TiO(2) particle growth on the order of 1 nm is observed. Despite a corresponding decrease of BET surface area, more dye is adsorbed onto the oxide surface. Although it seems trivial to match this finding with the improved photocurrent, this performance improvement cannot be attributed to higher dye adsorption only. This follows from comparison between incident photon to current conversion efficiency (IPCE) and light absorption characteristics. Since the charge transport properties of the TiO(2) films are already more than sufficient without treatment, the increase in short circuit current density J(SC) cannot be related to improvements in charge transport either. Transient photocurrent measurements indicate a shift in the conduction band edge of the TiO(2) upon TiCl(4) treatment. It is concluded that the main contribution to enhanced current originates from this shift in conduction band edge, resulting in improved charge injection into the TiO(2).     

Measuring charge transport from transient photovoltage rise times. A new tool to investigate electron transport in nanoparticle films

Charge transport rate at open-circuit potential (V(oc)) is proposed as a new characterization method for dye-sensitized (DS) and other nanostructured solar cells. At V(oc), charge density is flat and measurable, which simplifies quantitative comparison of transport and charge density. Transport measured at V(oc) also allows meaningful comparison of charge transport rates between different treatments, temperatures, and types of cells. However, in typical DS cells, charge transport rates at V(oc) often cannot be measured by photocurrent transients or modulation techniques due to RC limitations and/or recombination losses. To circumvent this limitation, we show that charge transport at V(oc) can be determined directly from the transient photovoltage rise time using a simple, zero-free-parameter model. This method is not sensitive to RC limitation or recombination losses. In trap limited devices, such as DS cells, the comparison of transport rates between different devices or conditions is only valid when the Fermi level in the limiting conductor is at the same distance from the band edge. We show how to perform such comparisons, correcting for conduction band shifts using the density of states (DOS) distribution determined from the same photovoltage transients. Last we show that the relationship between measured transport rate and measured charge density is consistent with the trap limited transport model.     

Dynamically corrected transition state theory calculations of self-diffusion in anisotropic nanoporous materials

We apply the dynamically corrected transition state theory to confinements with complex structures. This method is able to compute self-diffusion coefficients for adsorbate-adsorbent systems far beyond the time scales accessible to molecular dynamics. Two example cage/window-type confinements are examined: ethane in ERI- and CHA-type zeolites. In ERI-type zeolites, each hop in the z direction is preceded by a hop in xy direction and diffusion is anisotropic. The lattice for CHA-type zeolite is a rhombohedral Bravais lattice, and diffusion can be considered isotropic in practice. The anisotropic behavior of ERI-type cages reverses with loading, i.e., at low loading the diffusion in the z direction is two times faster than in the xy direction, while for higher loadings this changes to a z diffusivity that is more than two times slower. At low loading the diffusion is impeded by the eight-ring windows, i.e., the exits out of the cage to the next, but at higher loadings the barrier is formed by the center of the cages.     

Molecular order and disorder of surfactants in clay nanocomposites

Disorder of intercalated surfactant molecules in clay minerals causes gradual swelling, rather than commonly assumed swelling in discrete steps.     

Fatou Components of Attracting Skew-Products

We investigate the existence of wandering Fatou components for polynomial skew-products in two complex variables. In 2004, the non-existence of wandering domains near a super-attracting invariant fiber was shown in Lilov (Fatou theory in two dimensions, PhD thesis, University of Michigan, 2004). In 2014, it was shown in Astorg et al. (Ann Math, arXiv:1411.1188 [math.DS], 2014) that wandering domains can exist near a parabolic invariant fiber. In Peters and Vivas (Math Z, arXiv:1408.0498, 2014), the geometrically attracting case was studied, and we continue this study here. We prove the non-existence of wandering domains for subhyperbolic attracting skew-products; this class contains the maps studied in Peters and Vivas (Math Z, arXiv:1408.0498, 2014). Using expansion properties on the Julia set in the invariant fiber, we prove bounds on the rate of escape of critical orbits in almost all fibers. Our main tool in describing these critical orbits is a possibly singular linearization map of unstable manifolds.     

Temperature and size effects on diffusion in carbon nanotubes

We study the self-diffusion of simple gases inside single-walled carbon nanotubes at the zero-loading limit by molecular dynamics simulations. The host-framework flexibility influence is taken into account. In particular, we study the influences of nanotube size and temperature. For the carbon-nanotube radius-dependent self-diffusivities, a maximum is observed, which resembles the so-called levitation effect. This occurs for pores having a radius comparable to the position of the interaction-energy minimum. Surprisingly, the temperature influence is not uniform throughout different pore sizes. Diffusivities are expected to increase with temperature. This effect is observed for carbon nanotubes distinctly larger than the guest molecules. Remarkably, for smaller pores, the self-diffusivities decrease with increasing temperature or exhibit a maximum in the temperature dependence. This effect is caused by competing influences of collision frequency and temperature.     

Modeling of integrated extended cavity InP/InGaAsP semiconductor modelocked ring lasers

In this paper a model and simulation results of integrated semiconductor passively modelocked ring lasers are presented. The model includes nonlinear effects such as two-photon absorption and a non-linear refractive index, a logarithmic gain-carrier relation, and concentration dependent radiative and non-radiative carrier recombination rates. The optical bandwidth of the system is controlled by a digital filter. The model has been used to simulate two geometries of ring modelocked lasers. The first is a symmetric design, where the two counter propagating pulses in the cavity experience the same amplification and absorption. The second is an asymmetric design where the differences for the two directions of pulse propagation are maximised. Simulation results show that a symmetrical cavity shows a several times wider window for its operating parameters for stable modelocking.     

Application of adsorptive percolation to the analysis of hydrocarbon mixtures

A survey of the application of chromatograpinc analysis to mixtures of hydrocarbons has been given. An empirical constant called “transport factor” has been introduced. It is defined as the ratio of the weight of adsorbent contained in a certain column to the volume of developer necessary to transport the front of the adsorption band of a certain substance from the top of the column to its lower end. The transport factors on silicagel of five hydrocarbons in combination with several developers have been determined. A separation of a mixture of five hydrocarbons has been carried out using a series of three developers.The experimental “chromatogram” and the chromatogram calculated with the aid of the transport factors are in close agreement. In this way the transport factor may even serve as a means of identification.     

Cyanide und Halogene

Ohne Zusammenfassung