A reaction surface Hamiltonian study of malonaldehyde.

We report calculations using a reaction surface Hamiltonian for which the vibrations of a molecule are represented by 3N-8 normal coordinates, Q, and two large amplitude motions, s(1) and s(2). The exact form of the kinetic energy operator is derived in these coordinates. The potential surface is first represented as a quadratic in Q, the coefficients of which depend upon the values of s(1),s(2) and then extended to include up to Q(6) diagonal anharmonic terms.

Accurate computational determination of the binding energy of the SO3 x H2O complex.

Reliable thermochemical data for the reaction SO3 + H2O<-->SO3 x H2O (1a) are of crucial importance for an adequate modeling of the homogeneous H2SO4 formation in the atmosphere. We report on high-level quantum chemical calculations to predict the binding energy of the SO3 x H2O complex. The electronic binding energy is accurately computed to De = 40.

Evidence for laser-induced formation of solvated electrons in room temperature ionic liquids.

The photolytic generation of solvated electrons was observed for the first time in two room temperature ionic liquids (RTILs), trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide (IL) and 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide (IL). A 70 fs UV-pulse was used to excite the RTILs, while the transient response was monitored in the visible and near-infrared spectral regions. Immediately after excitation, a pulse duration limited rise of the induced absorption indicated the formation of solvated electrons suggesting the existence of pre-formed traps in RTILs.

Sulfamidation of 2-arylaldehydes and ketones with chloramine-T.

[reaction: see text] A series of aliphatic and aromatic carbonyl compounds has been transformed into the corresponding sulfamidated products by means of amine-catalyzed nitrene transfer of chloramine-T. Depending on the residues R, either alpha-sulfamidation in the case of aromatic aldehydes and acetone derivatives or direct sulfamidation at the carbonyl functionality of aliphatic aldehydes has been observed. Applying microwave conditions, good to excellent yields under significantly reduced reaction times could be obtained, thus providing a facile access to alpha,alpha-disubstituted amino acids.

Second-harmonic generation from magnetic metamaterials.

We observe second-harmonic generation from metamaterials composed of split-ring resonators excited at 1.5-micrometer wavelength. Much larger signals are detected when magnetic-dipole resonances are excited, as compared with purely electric-dipole resonances.

Growing graphene sheets from reactions with methyl radicals: a quantum chemical study.

Hydrogen abstraction reactions by methyl radicals on the zigzag and armchair edges of perylene are studied by density functional theory (DFT) to explore various growth pathways that seem to be in line with experimental observations. The DFT approach is validated by comparing the results obtained from calculations with six different functionals with those obtained from correlated ab initio methods, thereby emphasizing the calculation of reaction barriers. A useful compromise between accuracy and computational cost is provided by DFT, and possible pathways are studied in detail at this level of calculation.

In-situ voltage tunneling spectroscopy at electrochemical interfaces.

Nanophysics at electrochemical interfaces, probing the physical properties of nanostructures, requires laterally resolved in-situ spectroscopy, in particular voltage tunneling spectroscopy (VTS), which is at present not yet established. In-situ spectroscopy is required to achieve reliable and reproducible measurements of the intrinsic properties of nanostructures in an electrochemical environment, which are mainly determined in small nanostructures by surface atoms rather than bulk atoms. In contrast to tunneling spectroscopy in ultrahigh vacuum, tip and substrate double-layer capacitances as well as Faradaic currents play an important role in voltage tunneling spectroscopy at electrochemical interfaces.

Thermochemical properties, rotation barriers, and group additivity for unsaturated oxygenated hydrocarbons and radicals resulting from reaction of vinyl and phenyl radical systems with O2.

Oxidation of unsaturated and aromatic hydrocarbons in atmospheric and combustion processes results in formation of linear and cyclic unsaturated, oxygenated-hydrocarbon intermediates. The thermochemical parameters delatafH degrees 298, S degrees 298, and C(p)(f298)(T) for these intermediates are needed to understand their stability and reaction paths in further oxidation. These properties are not available for a majority of these unsaturated oxy-hydrocarbons and their corresponding radicals, even via group additivity methods.

Monitoring the formation of an Aureobasidium pullulans biofilm in a bead-packed reactor via flow-weighted magnetic resonance imaging.

The biofilm-forming fungus, Aureobasidium pullulans DSM 2404, was grown in a bead-packed reactor. Alterations within the reactor were analysed in several cross-sectional slices by magnetic resonance imaging (MRI) with flow contrast. For the first time, biofilm accumulation could be continuously elucidated without using any contrast agents, and the non-stationary flow through the fixed-bed reactor could be visualized.

Observation and modelling of barrel droplets on vertical fibres subjected to gravitational and drag forces.

Extensive experimental investigation of the wetting processes of fibre/liquid systems during air filtration (when drag and gravitational forces are acting) has shown many important features, including droplet extension, oscillatory motion, and detachment or flow of drops from fibres as airflow velocity increases. A detailed experimental study of the aforementioned processes was conducted using glass filter fibres and H(2)O aerosol, which coalesce on the fibre to form barrel droplets with small contact angles. The droplets were predominantly observed in the Reynolds transition (or unsteady laminar) flow region.

Lewis acid stabilized OPI3: implications for the nature of free OPI3.

While reinvestigating the published synthesis of OPI(3), it became evident from the experiments that phosphoryl triodide may only be formed as an intermediate and that the end products of the reaction of OPCl(3) with LiI are P(V) oxides, PI(3), I(2), and LiCl. This is also in agreement with MP2/TZVPP calculations, which assign Delta(r)H degrees (Delta(r)G degrees ) [Delta(r)G degrees in CHCl(3)] for the disproportionation of OPI(3) as -7 (-18) [-17 kJ mol(-1)] (assuming P(4)O(10) as the P(V) oxide). The first products of this reaction visible in a low-temperature in situ (31)P NMR experiment are P(2)I(4) and PI(3), as well as traces of a compound that may be OPCl(2)I.

High-pressure liquid dispersion and fragmentation of flame-made silica agglomerates.

The influence of primary particle diameter and the degree of agglomeration of flame-made silica agglomerate suspensions in aqueous solutions is studied by high-pressure dispersion (up to 1500 bar) through a nozzle with a 125 microm inner diameter. These particles were produced (4-15 g/h) by oxidation of hexamethyldisiloxane (HMDSO) in a coflow diffusion flame reactor. Their average primary particle size (10-50 nm) and degree of agglomeration were controlled by varying the oxygen and precursor flow rates.

Advances in the production of sponge biomass Aplysina aerophoba--a model sponge for ex situ sponge biomass production.

Sponges are a promising source of organic compounds of potential interest regarding industrial and medical applications. For detailed studies on such compounds, large amounts of sponge biomass are required. Obtaining that is at present extremely difficult because most sponges are relatively rare in nature and their mass cultivation in the laboratory has not yet been accomplished.

Simultaneous negative phase and group velocity of light in a metamaterial.

We investigated the propagation of femtosecond laser pulses through a metamaterial that has a negative index of refraction for wavelengths around 1.5 micrometers. From the interference fringes of a Michelson interferometer with and without the sample, we directly inferred the phase time delay.

Density functional study of methyl chemisorption on polycyclic aromatic hydrocarbons.

The reactions of methyl radicals with large (up to C(96)H(24)) polycyclic aromatic hydrocarbons (PAHs) are studied by density functional calculations to shed light on the experimentally observed deposition of carbon on highly oriented pyrolytic graphite (HOPG), which occurs when hot HOPG (decorated by nanometre-sized defects) is exposed to methyl radicals. The equilibrium structures of the reaction products, together with transition structures for PAHs up to the size of phenanthroperylene, are determined using the density functionals B3LYP, TPSSh, BP86 and TPSS. The structures are analysed by computing the pi orbital axis vector (POAV) and the altitude of the reactive carbon above the molecular plane of the PAH.

High-repetition-rate white-light pump-probe spectroscopy with a tapered fiber.

We have realized a 76 MHz white-light differential transmission spectroscopy system. The technique employs a Ti:sapphire laser oscillator and a tapered fiber to generate a white-light continuum spanning almost the full visible to near-infrared spectral range. Using acousto-optical modulation and subsequent lock-in detection, transient relative transmission changes as small as 10(-5) are detected.

Influence of electrophysiological heterogeneity on electrical stimulation in healthy and failing human hearts.

The application of strong electrical stimuli is a common method used for terminating irregular cardiac behaviour. The study presents the influence of electrophysiological heterogeneity on the response of human hearts to electrical stimulation. The human electrophysiology was simulated using the ten Tusscher-Noble-Noble-Panfilov cell model.

3D-2D-3D photonic crystal heterostructures fabricated by direct laser writing.

Using direct laser writing, we fabricate photoresist templates for 3D-2D-3D photonic crystal heterostructures for what we believe to be the first time. The optical properties of these structures are directly compared with the theoretical ideal, revealing good agreement and hence good sample quality. This provides an experimental starting point for the microfabrication and testing of broadband, 3D air-waveguide microcircuitry in photonic bandgap materials.

Comparison of leaching tests to determine and quantify the release of inorganic contaminants in demolition waste.

The changes in waste management policy caused by the massive generation of waste materials (e.g. construction and demolition waste material, municipal waste incineration products) has led to an increase in the reuse and recycling of waste materials.

Diastereoselective synthesis of highly functionalized tetrahydroxanthenols--unprecedented access to privileged structural motifs.

Tetrahydroxanthenones, which can be easily prepared by a domino oxa-Michael aldol condensation, offer various possibilities for diastereoselective functionalization, giving access to the stereocontrolled synthesis of stereochemical triades or tetrades, which represent privileged structural motifs. In most cases, the relative stereochemistry was unequivocally established by crystal structure analysis.

Three-dimensional cylindrical X-band ESR imaging by a combined pulsed gradient Fourier and static gradient projection reconstruction method.

Static gradient electron spin echo projection reconstruction imaging is favourable for X-band material science applications requiring temperature variation with a metal cryostat. To prevent imaging artefacts due to the high conduction electron diffusion coefficient in the preferred conduction direction of quasi-one-dimensional conductors, only pulsed gradient phase encoding for that direction can be tolerated. We present results of an appropriate cylindrical imaging scheme combining both methods.

Conduction-electron drift velocity measurement via electron spin resonance.

In analogy with NMR, motion induced phase shift of pulsed ESR signals enables in principle the direct detection of electron drift velocity or electronic current, respectively. Overcoming the difficulties with additional magnetic field gradients induced by the current itself, we succeeded in demonstrating the detection of electron flow via ESR. Measuring the electron drift velocity in the organic conductor (fluoranthene)2PF6 the microscopic Ohmic law could be observed in a current range of more than +/-0.