Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH

We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(v), D + FD(v), H + FD(v), and D + FH(v) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number v and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin’s three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(v) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with v→v−1 processes dominating

Nonequilibrium Critical Dynamics of a Three Species Monomer-Monomer Model

We study a three species monomer-monomer catalytic surface reaction model with a reactive steady state bordered by three equivalent unreactive phases where the surface is saturated with one species. The transition from the reactive to a saturated phase shows directed percolation critical behavior. Each pair of these reactive-saturated phase boundaries join at a bicritical point where the universal behavior is in the even branching annihilating random walk class. We find the crossover exponent from bicritical to critical behavior and a new exponent associated with the bicritical interface dynamics.Comment: 4 pages RevTex. 4 eps figures included with psfig.sty. Uses multicol.sty. Accepted for publication in PR

Reactive infiltration instability amplifies the difference between geometric and reactive surface areas in natural porous materials

Reactive infiltration instability (RII) drives the development of many natural and engineered flow systems. These are encountered e.g. in hydraulic fracturing, geologic carbon storage and well stimulation in enhanced oil recovery. The surface area of the rocks changes as the pore structure evolves. We combined a reactor network model with grey scale tomography to seek the morphological interpretation for differences among geometric, reactive and apparent surface areas of dissolving natural porous materials. The approach allowed us to delineate the experimentally convoluted variables and study independently the effects of initial geometry and macroscopic flowrate. Simulations based on North Sea chalk microstructure showed that geometric surface not only serves as the interface for water-rock interactions but also represents the regional transport heterogeneities that can be amplified indefinitely by dissolutive percolation. Hence, RII leads to channelization of the solid matrix, which results in fluid focusing and an increase in geometric surface area. Fluid focusing reduces the reactive surface area and the residence time of reactants, both of which amplify the differences in question, i.e. they are self-supporting. Our results also suggested that the growing and merging of microchannels near the fluid entrance leads to the macroscopic "fast initial dissolution" of chemically homogeneous materials.Comment: 37 pages, 12 figure

Arbitrary beam control using passive lossless metasurfaces enabled by orthogonally-polarized custom surface waves

For passive, lossless impenetrable metasurfaces, a design technique for arbitrary beam control of receiving, guiding, and launching is presented. Arbitrary control is enabled by a custom surface wave in an orthogonal polarization such that its addition to the incident (input) and the desired scattered (output) fields is supported by a reactive surface impedance everywhere on the reflecting surface. Such a custom surface wave (SW) takes the form of an evanescent wave propagating along the surface with a spatially varying envelope. A growing SW appears when an illuminating beam is received. The SW amplitude stays constant when power is guided along the surface. The amplitude diminishes as a propagating wave (PW) is launched from the surface as a leaky wave. The resulting reactive tensor impedance profile may be realized as an array of anisotropic metallic resonators printed on a grounded dielectric substrate. Illustrative design examples of a Gaussian beam translator-reflector, a probe-fed beam launcher, and a near-field focusing lens are provided

Vapor phase surface functionalization under ultra violet activation of parylene thin films grown by chemical vapor deposition

Various reactive gas phase treatments have been investigated as surface functionalization dry processes with the goal to improve the wettability of parylene C films, keeping good optical properties in the visible range. The films were grown on different substrates by chemical vapor deposition with thicknesses ranging from 300 to 1630 nm. The polymer surface was treated under ultra violet (UV) irradiation at 254 nm in reactive atmospheres including He, H2O, H2O2, O2 and ambient air. The UV/O2 treatment is the most efficient since the water contact angle decreases from 100° to 6° while the transmittance is maintained at 90% in the visible wavelengths. Furthermore it exhibits long life stability. The functionalization mechanism is discussed in relation with previous reports

Thin film diffusion barrier formation in PDMS microcavities

We describe a method to form glass like thin film barrier in polydimethylsiloxane (PDMS) microcavities. The reactive fragments for the surface reaction were created from O2 and hexamethyldisiloxane (HMDS) in RF plasma environment. The reaction is based on migration of the reactive fragments into the microcavities by diffusion, to form a glass like thin film barrier to conceal the naked surface of PDMS. The barrier successfully blocked penetration of a fluorescent dye rhodamine B (RhB) into PDMS. The thickness of the barrier could be controlled by the time of reaction and the pressure inside the reaction chamber. There is a wide range of applications of such a technique in various fields, e.g. for coating the covered surfaces of microfluidic channels, tubes, capillaries, medical devices, catheters, as well as chip-integrated capillary electrophoresis and advanced electronic and opto-fluidic packaging

Kinetics and mechanism of formic acid decomposition on Ru(001)

The steady-state rate of decomposition of formic acid on Ru(001) has been measured as a function of surface temperature, parametric in the pressure of formic acid. The products of the decomposition reaction are C0_2, H_2, CO, and H_2)0, i.e., both dehydrogenation and dehydration occur on Ru (001). A similar product distribution has been observed on Ni(110), Ni(100), Ru(100), Fe(100), and Ni(111) surfaces; whereas only dehydrogenation to C0_2 and H_2 occurs on the Cu(100), Cu(110), and Pt(111) surfaces. Only reversible adsorption and desorption of formic acid is observed on the less reactive Ag(110) surface at low temperatures, whereas the more reactive Mo(100) surface is oxidized by formic acid at low temperatures with the products of this reaction being H_2, CO, and H_(2)O (Ref. 10). We report here the confirmation of earlier observations of the occurrence of both dehydrogenation and dehydration of formic acid on Ru(001), and more importantly, we provide a detailed mechanistic description of the steady-state decomposition reaction on this surface in terms of elementary steps

The three species monomer-monomer model in the reaction-controlled limit

We study the one dimensional three species monomer-monomer reaction model in the reaction controlled limit using mean-field theory and dynamic Monte Carlo simulations. The phase diagram consists of a reactive steady state bordered by three equivalent adsorbing phases where the surface is saturated with one monomer species. The transitions from the reactive phase are all continuous, while the transitions between adsorbing phases are first-order. Bicritical points occur where the reactive phase simultaneously meets two adsorbing phases. The transitions from the reactive to an adsorbing phase show directed percolation critical behaviour, while the universal behaviour at the bicritical points is in the even branching annihilating random walk class. The results are contrasted and compared to previous results for the adsorption-controlled limit of the same model.Comment: 12 pages using RevTeX, plus 4 postscript figures. Uses psfig.sty. accepted to Journal of Physics

First-principles statistical mechanics study of the stability of a sub-nanometer thin surface oxide in reactive environments: CO oxidation at Pd(100)

We employ a multiscale modeling approach to study the surface structure and composition of a Pd(100) model catalyst in reactive environments. Under gas phase conditions representative of technological CO oxidation (~1 atm, 300-600 K) we find the system on the verge of either stabilizing sub-nanometer thin oxide structures or CO adlayers at the surface. Under steady-state operation this suggests the presence or continuous formation and reduction of oxidic patches at the surface, which could be key to understand the observable catalytic function.Comment: 4 pages including 2 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Exact Results for Kinetics of Catalytic Reactions

The kinetics of an irreversible catalytic reaction on substrate of arbitrary dimension is examined. In the limit of infinitesimal reaction rate (reaction-controlled limit), we solve the dimer-dimer surface reaction model (or voter model) exactly in arbitrary dimension $D$. The density of reactive interfaces is found to exhibit a power law decay for $D<2$ and a slow logarithmic decay in two dimensions. We discuss the relevance of these results for the monomer-monomer surface reaction model.Comment: 4 pages, RevTeX, no figure