Chiral surface characterisation and reactivity toward H-D exchange of a curved platinum crystal

Understanding heterogeneous catalysis at the atomic level requires detailed knowledge of the reactivity of different surface sites toward specific bond breaking and bond making events. We illustrate a new method in such investigations. We use a macroscopically curved Pt single crystal containing a large variation in density of highly kinked steps of two different chiralities. Scanning tunneling microscopy maps the entire range of surface structures present on the 31 degrees section surrounding the Pt(111) apex. Whereas most of the surface shows the expected characteristic arrays of parallel steps, hexagonally-shaped, single-atom deep pits remain after cleaning procedures near the apex. Their orientation is indicative of the different chiralities present on the two sides of the crystal's apex. These unintended defects locally raise the surface defect concentration, but are of little consequence to subsequent reactivity measurements for D-2 dissociation and H-D exchange as probed by supersonic molecular beam techniques. We quantify absolute elementary dissociation and relative isotopic exchange rates across the surface with high spatial resolution. At low incident energies, elementary dissociation of the homonuclear isotoplogues is dominated by the kinked steps. H-D exchange kinetics depend also mostly linearly on step density. The changing ratio of D(2)dissociation to H-D formation, however, suggests that anisotropic diffusion of H(D) atoms is of influence to the measured HD production rate.Catalysis and Surface Chemistr

Employment in Personality Disorders and the Effectiveness of Individual Placement and Support:Outcomes from a Secondary Data Analysis

Purpose Personality disorders (PDs) are associated with severe functional impairment and subsequent high societal costs, increasing the need to improve occupational functioning in PD. Individual placement and support (IPS) is an effective, evidence-based method of supported employment, which so far has been tested in various mixed patient populations with severe mental illness (SMI, including PDs). However, the effectiveness of IPS for PDs per se remains uninvestigated. Methods Data from the SCION trial were used, including 31 SMI patients with PDs and 115 SMI patients with other primary diagnoses (primarily psychotic disorders). First, the interaction effect of diagnosis (PD vs other SMI) and intervention (IPS vs traditional vocational rehabilitation) was studied. Second, in the IPS condition, difference between diagnostic groups in time to first job was studied. Results We did not find evidence of a moderating effect of PD diagnosis on the primary effect of IPS (proportion who started in regular employment) (OR = 0.592, 95% CI 0.80–4.350, p = 0.606) after 30 months. Also, PD diagnosis did not moderate the effect of time until first job in IPS. Conclusions From the present explorative analysis we did not find evidence for a moderating effect of PD diagnosis on the effectiveness of IPS among PD participants. This indicates that IPS could be as effective in gaining employment in participants with PD as it is in participants with other SMI. Future studies, implementing larger numbers, should confirm whether IPS is equally effective in PDs and study whether augmentations or alterations to the standard IPS model might be beneficiary for PD

Coverage-dependent adsorption and desorption of oxygen on Pd(100)

Catalysis and Surface Chemistr

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

Double-Stranded Water on Stepped Platinum Surfaces

The interaction of platinum with water plays a key role in (electro)catalysis. Herein, we describe a combined theoretical and experimental study that resolves the preferred adsorption structure of water wetting the Pt(111)-step type with adjacent (111) terraces. Double stranded lines wet the step edge forming water tetragons with dissimilar hydrogen bonds within and between the lines. Our results qualitatively explain experimental observations of water desorption and impact our thinking of solvation at the Pt electrochemical interface

Cholinesterase Inhibitors and Hospitalization for Bradycardia: A Population-Based Study

Laura Park-Wyllie and colleagues examined the health records of more than 1.4 million older adults and show that initiation of cholinesterase inhibitor therapy is associated with a more than doubling of the risk of hospitalization for bradycardia

Scaling platinum‐catalyzed hydrogen dissociation on corrugated surfaces

We determine absolute reactivities for dissociation at low coordinated Pt sites. Two curved Pt(111) single-crystal surfaces allow us to probe either straight or highly kinked step edges with molecules impinging at a low impact energy. A model extracts the average reactivity of inner and outer kink atoms, which is compared to the reactivity of straight A- and B-type steps. Local surface coordination numbers do not adequately capture reactivity trends for H(2)dissociation. We utilize the increase of reactivity with step density to determine the area over which a step causes increased dissociation. This step-type specific reactive area extends beyond the step edge onto the (111) terrace. It defines the reaction cross-section for H(2)dissociation at the step, bypassing assumptions about contributions of individual types of surface atoms. Our results stress the non-local nature of H(2)interaction with a surface and provide insight into reactivity differences for nearly identical step sites.Catalysis and Surface Chemistr

IR spectroscopic characterization of the co-adsorption of CO2 and H2 onto cationic Cun+ clusters

NWOTheoretical Chemistr

Step-type and step-density influences on CO adsorption probed by reflection absorption infrared spectroscopy using a curved Pt(1 1 1) surface

In comparison to flat single crystals, the continuous variation of structure provided by curved crystals offers many benefits for the study of physical and chemical processes at surfaces. However, the curvature of the surface also creates experimental challenges. For infrared spectroscopy, in particular, adsorbates on metal samples are typically probed by grazing-incidence reflection-absorption infrared spectroscopy (RAIRS). In this geometry, a convex crystal acts as a strongly diverging mirror. The authors describe how the experimental difficulties introduced by a cylindrical surface can be resolved for RAIRS. A complementary mirror, placed directly downfield of the curved crystal within the vacuum chamber, minimizes the divergence created by the sample. By simply translating the infrared focus across the sample, the authors probe adsorbate vibrational spectra as a function of local step-type and step-density with high sensitivity and spatial resolution. Time-consuming sample exchange, and the concomitant sample-to-sample experimental errors, are eliminated. The authors apply this new technique to carbon monoxide adsorption on a curved Pt(1 1 1) crystal and use it to resolve the influence of step-type and step-density on the CO stretch vibration as a function of coverage.</p