Bond breaking in vibrationally excited methane on transition metal catalysts

The role of vibrational excitation of a single mode in the scattering of methane is studied by wave packet simulations of oriented CH4 and CD4 molecules from a flat surface. All nine internal vibrations are included. In the translational energy range from 32 up to 128 kJ/mol we find that initial vibrational excitations enhance the transfer of translational energy towards vibrational energy and increase the accessibility of the entrance channel for dissociation. Our simulations predict that initial vibrational excitations of the asymmetrical stretch (nu_3) and especially the symmetrical stretch (nu_1) modes will give the highest enhancement of the dissociation probability of methane.Comment: 4 pages REVTeX, 2 figures (eps), to be published in Phys. Rev. B. (See also arXiv:physics.chem-ph/0003031). Journal version at http://publish.aps.org/abstract/PRB/v61/p1565

Comparison of Venae Sectio vs. modified Seldinger Technique for Totally Implantable Access Ports; Portas-trial [ISRCTN:52368201]

BACKGROUND: The insertion of a Totally Implantable Access Port (TIAP) is a routinely employed technique in patients who need a safe and permanent venous access. The number of TIAP implantations is increasing constantly mainly due to advanced treatment options for malignant diseases. Therefore it is important to identify the implantation technique which has the optimal benefit/risk ratio for the patient. STUDY DESIGN: A single-centre, randomized, controlled superiority trial to compare two different TIAP implantation techniques. Sample size: 160 patients will be included and randomized intra-operatively. Eligibility criteria: Age equal or older than 18 years, patients scheduled for primary elective implantation of a TIAP in local anaesthesia and a signed informed consent. Primary endpoint: Primary success rate of the randomized technique. Intervention: Venae Sectio in combination with the Seldinger Technique (guide wire and a peel away sheath) will be used to place a TIAP. Reference treatment: Conventional Venae Sectio will be used with a direct insertion of the TIAP without guide wire or peel away sheath. Duration of study: Approximately 20 months. ORGANISATION/RESPONSIBILITY: The trial will be conducted in compliance with the protocol and in accordance with the moral, ethical, and scientific principles governing clinical research as set out in the Declaration of Helsinki (1989) and Good Clinical Practice (GCP). The trial will also be carried out in keeping with local and regulatory requirements. The Klinisches Studienzentrum Chirurgie (KSC) – Centre of Clinical Trials in Surgery at the Department of Surgery, University Hospital Heidelberg is responsible for planning and conduction of the trial. Documentation of patient's data will be accomplished via electronical Case Report Files (eCRF) with MACRO(®)-Software by the KSC. Randomization, data management, monitoring and biometry are provided by the independent Koordinierungszentrum für Klinische Studien (KKS) – Coordination Centre for Clinical Trails at the University of Heidelberg

Disruption of host-seeking behaviour by the salmon louse,Lepeophtheirus salmonis,using botanically derived repellents

The potential for developing botanically derived natural products as novel feed-through repellents for disrupting settlement of the salmon louse, Lepeophtheirus salmonis (Caligidae) upon farmed Atlantic salmon, Salmo salar, was investigated using an established laboratory vertical Y-tube behavioural bioassay for assessing copepodid behaviour. Responses to artificial sea water conditioned with the odour of salmon, or to the known salmon-derived kairomone component, α-isophorone, in admixture with selected botanical materials previously known to interfere with invertebrate arthropod host location were recorded. Materials included oils extracted from garlic, Allium sativum (Amaryllidaceae), rosemary, Rosmarinus officinalis (Lamiaceae), lavender, Lavandula angustifolia (Lamiaceae), and bog myrtle, Myrica gale (Myricaceae), and individual components (diallyl sulphide and diallyl disulphide from garlic; allyl, propyl, butyl, 4-pentenyl and 2-phenylethyl isothiocyanate from plants in the Brassica genus). Removal of attraction to salmon-conditioned water (SCW) or α-isophorone was observed when listed materials were presented at extremely low parts per trillion (ppt), that is picograms per litre or 10−12 level. Significant masking of attraction to SCW was observed at a level of 10 ppt for diallyl disulphide and diallyl sulphide, and allyl isothiocyanate and butyl isothiocyanate. The potential of very low concentrations of masking compounds to disrupt Le. salmonis copepodid settlement on a host fish has been demonstrated in vitro

Ab initio Quantum and ab initio Molecular Dynamics of the Dissociative Adsorption of Hydrogen on Pd(100)

The dissociative adsorption of hydrogen on Pd(100) has been studied by ab initio quantum dynamics and ab initio molecular dynamics calculations. Treating all hydrogen degrees of freedom as dynamical coordinates implies a high dimensionality and requires statistical averages over thousands of trajectories. An efficient and accurate treatment of such extensive statistics is achieved in two steps: In a first step we evaluate the ab initio potential energy surface (PES) and determine an analytical representation. Then, in an independent second step dynamical calculations are performed on the analytical representation of the PES. Thus the dissociation dynamics is investigated without any crucial assumption except for the Born-Oppenheimer approximation which is anyhow employed when density-functional theory calculations are performed. The ab initio molecular dynamics is compared to detailed quantum dynamical calculations on exactly the same ab initio PES. The occurence of quantum oscillations in the sticking probability as a function of kinetic energy is addressed. They turn out to be very sensitive to the symmetry of the initial conditions. At low kinetic energies sticking is dominated by the steering effect which is illustrated using classical trajectories. The steering effects depends on the kinetic energy, but not on the mass of the molecules. Zero-point effects lead to strong differences between quantum and classical calculations of the sticking probability. The dependence of the sticking probability on the angle of incidence is analysed; it is found to be in good agreement with experimental data. The results show that the determination of the potential energy surface combined with high-dimensional dynamical calculations, in which all relevant degrees of freedon are taken into account, leads to a detailed understanding of the dissociation dynamics of hydrogen at a transition metal surface.Comment: 15 pages, 9 figures, subm. to Phys. Rev.

Possible implications of the channeling effect in NaI(Tl) crystals

The channeling effect of low energy ions along the crystallographic axes and planes of NaI(Tl) crystals is discussed in the framework of corollary investigations on WIMP Dark Matter candidates. In fact, the modeling of this existing effect implies a more complex evaluation of the luminosity yield for low energy recoiling Na and I ions. In the present paper related phenomenological arguments are developed and possible implications are discussed at some extent.Comment: 16 pages, 10 figures, preprint ROM2F/2007/15, submitted for publicatio

To bite or not to bite! A questionnaire-based survey assessing why some people are bitten more than others by midges

BACKGROUND: The Scottish biting midge, Culicoides impunctatus, responsible for more than 90% of biting attacks on human beings in Scotland, is known to demonstrate a preference for certain human hosts over others. METHODS: In this study we used a questionnaire-based survey to assess the association between people's perception of how badly they get bitten by midges and their demographic, lifestyle and health related characteristics. RESULTS: Most people (85.8%) reported being bitten sometimes, often or always with only 14.2% reporting never being bitten by midges when in Scotland. There was no association between level of bites received and age, smoking, diet, exercise, medication, eating strongly flavoured foods or alcohol consumption. However, there was a strong association between the probability of being bitten and increasing height (in men) and BMI (in women). A large proportion of participants (33.8%) reported experiencing a bad/severe reaction to midge bites while 53.1% reported a minor reaction and 13.1% no reaction at all. Also, women tend to react more than men to midge bites. Additionally, the results indicated that the susceptibility to being bitten by midges is hereditary. CONCLUSIONS: This study suggests that midges prefer to bite men that are tall and women that have a large BMI, and that the tendency for a child to be bitten or not could be inherited from their parent. The study is questionnaire-based; therefore, the interpretation of the results may be limited by the subjectivity of the answers given by the respondents. Although the results are relevant only to the Scottish biting midge, the approach used here could be useful for investigating human-insect interactions for other insects, particularly those which transmit pathogens that cause disease

Ultrafast adsorbate excitation probed with sub-ps resolution XAS

We use a pump-probe scheme to measure the time evolution of the C K-edge X-ray absorption spectrum (XAS) from CO/Ru(0001) after excitation by an ultrashort high-intensity optical laser pulse. Due to the short duration of the X-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first ps after the pump can be resolved with unprecedented time resolution. By comparing with theoretical (DFT) spectrum calculations we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the ps regime. The ~100 fs initial excitation of these CO vibrational modes is not readily rationalized by traditional theories of nonadiabatic coupling of adsorbates to metal surfaces, e. g. electronic frictions based on first order electron-phonon coupling or transient population of adsorbate resonances. We suggest that coupling of the adsorbate to non-thermalized electron-hole pairs is responsible for the ultrafast initial excitation of the modes.Comment: 16 pages, 16 figures. To be published in Physical Review Letters: https://journals.aps.org/prl/accepted/c1070Y74M8b18063d9cd0221b000631d50ef7a24

Ultrafast Adsorbate Excitation Probed with Subpicosecond-Resolution X-Ray Absorption Spectroscopy

We use a pump-probe scheme to measure the time evolution of the C K-edge x-ray absorption spectrum from CO/Ru(0001) after excitation by an ultrashort high-intensity optical laser pulse. Because of the short duration of the x-ray probe pulse and precise control of the pulse delay, the excitation-induced dynamics during the first picosecond after the pump can be resolved with unprecedented time resolution. By comparing with density functional theory spectrum calculations, we find high excitation of the internal stretch and frustrated rotation modes occurring within 200 fs of laser excitation, as well as thermalization of the system in the picosecond regime. The ∼100  fs initial excitation of these CO vibrational modes is not readily rationalized by traditional theories of nonadiabatic coupling of adsorbates to metal surfaces, e.g., electronic frictions based on first order electron-phonon coupling or transient population of adsorbate resonances. We suggest that coupling of the adsorbate to nonthermalized electron-hole pairs is responsible for the ultrafast initial excitation of the modes