How low can you go? Minimum energy pathways for O2 dissociation on Pt(111).

Many DFT studies of O(2) dissociation on Pt(111) give conflicting information on preferred paths and final states. Here we report large p(4 × 4) unit cell minimum energy pathway evaluations and compare O(2) adsorption and dissociated states on Pt(111). Calculations reveal how the pathways for O(2) dissociation starting from top-fcc-bridge, top-hcp-bridge, and top-bridge-top sites are interconnected. They also provide a direct reaction pathway for the dissociation of an O(2) molecule from a top-fcc-bridge into an hcp and an fcc site, which is consistent with low temperature scanning tunneling microscope experiments. Such a pathway is shown to be considerably perturbed by the presence of co-adsorbed oxygen atoms. We quantify the coverage dependence through the construction of a Brønsted-Evans-Polanyi relationship relating the O(2) dissociation activation energies to the binding energies of the dissociated O atoms. We also show that all pathways starting from a top-fcc-bridge site give the smallest barriers for O(2) dissociation.

Effect of ultrafast diffusion on adsorption, desorption, and reaction processes over heterogeneous surfaces.

The effect of ultrafast diffusion is studied on reaction-diffusion processes in heterogeneous media, as encountered in catalysis and field emission microscopy. The reaction-diffusion equations describe adsorption, desorption, and reaction processes for two adspecies, for instance, on a paraboloidal heterogeneous surface in the presence of an external electric field. Using multiscale analysis, we show that the fast adspecies rapidly reaches a quasiequilibrium spatial distribution, characterized by a nonequilibrium chemical potential of the fast adspecies. An ordinary differential equation is derived for the time evolution of the nonequilibrium chemical potential. Numerical simulations are performed under different conditions, which confirm the convergence of the dynamics for finite diffusion toward the ultrafast diffusion limit predicted by our multiscale analysis. The numerical simulations also demonstrate that electric fields may induce important diffusive currents on heterogeneous surfaces under the conditions of field emission microscopy.

Catalytic reduction of NO2 with hydrogen on Pt field emitter tips: kinetic instabilities on the nanoscale.

The catalytic reduction of NO(2) with hydrogen on a Pt field emitter tip is investigated using both field electron microscopy (FEM) and field ion microscopy (FIM). A rich variety of nonlinear behavior and unusually high catalytic activity around the {012} facets are observed. Our FEM investigations reveal that the correlation function exhibits damped oscillations with a decaying envelope, showing that molecular noise will influence the dynamics of the oscillations. The dependence of the oscillatory period on the P(H(2))/P(NO(2)) pressure ratios is analyzed. Similar patterns are reported under FIM conditions. Corresponding density functional theory (DFT) calculations for the adsorption of NO(2) on Pt{012} in the presence of an external electric field are performed in order to gain an atomistic understanding of the underlying nonlinear phenomena.

Interaction between silver nanowires and CO on a stepped platinum surface.

We studied the interplay between Ag decoration of a stepped Pt(355) surface and CO adsorption by in situ high-resolution x-ray photoelectron spectroscopy. Varying amounts of Ag deposited at 300 K initially lead to a row-by-row growth starting from the lower Pt step edges. Such decoration of the step sites results in a change in the CO adsorption behavior. An apparent blocking of step sites for low CO coverages is attributed to a change in the electronic structure, resulting in a C 1s binding energy of CO at step sites being equal to that for CO at terrace on-top sites in the presence of Ag. Higher CO coverages induce the formation of embedded Ag clusters within the upper terraces, thus freeing up a part of the original Pt step sites for CO adsorption, as was derived by a comparison to density functional theory calculations in the corresponding surface models.

Phase diagram and adsorption-desorption kinetics of CO on Ru(0001) from first principles.

A kinetic lattice gas model is used to study the equilibrium properties and the desorption kinetics of CO on Ru(0001). The authors compute all relevant on-site binding and interaction energies of CO molecules within density functional theory and import them in two different models. The first model allows the CO molecules to adsorb upright on top and hollow sites. The authors calculate the phase diagram, coverage isobars, and temperature programed desorption spectra. Up to a coverage of 1/3 ML, very good agreement is obtained between theory and experiment when considering top sites only. For coverages beyond 1/3 ML, hollow sites are included and disagreement between theory and experiment occurs. The second model allows adsorption on top sites only but allows them to tilt and shift from their upright positions. The authors show that this model resolves many of the deficiencies of their first one. Furthermore, the authors demonstrate that this model is more consistent with experiment since it is the only model that is able to explain the results from IR-spectroscopy experiments.

CO oxidation on electrically charged gold nanotips.

We report a study of the oxidation of CO on a gold nanotip in the presence of high electrostatic fields. With the binding energies obtained using density functional theory as a function of the electric field, a simple field-dependent kinetic model based on the Langmuir-Hinshelwood mechanism is set up. We show that the dissociative adsorption of oxygen on gold happens only below a negative critical value of the electric field while the binding of CO on gold is enhanced for positive values. We explain the propagation of a wave observed in field ion microscopy experiments and predict that the oxidation of CO occurs on negatively charged gold clusters.

Two-dimensional roughening of adsorbate islands in thermodynamic equilibrium.

Equilibrium fluctuations of islands of adsorbed O atoms on Ru(0001) were investigated by scanning tunneling microscopy (STM), density functional theory calculations (DFT) and Monte Carlo (MC) simulations. Very ramified (2 x 2)-O islands were observed by high-speed STM that point to complex interactions between the O atoms. The DFT calculations show that, in addition to pairwise attractive interactions between third-nearest neighbors, a repulsive three-body interaction exists between these. MC simulations that include three-body interactions reproduce the observed ordering behavior.