Effect of substituents and hydrogen bonding on barrier heights in dehydration reactions of carbon and silicon geminal diols

Activation barrier heights for the dehydration reaction of geminal carbinols and silanediols R'R″X(OH)(2) (X = C, Si) were estimated at the B3LYP and MP2 levels of theory employing Dunning's correlation-consistent triple-zeta basis sets. It was shown that the barrier height for carbon derivatives steadily decreases upon substitution by R groups, usually termed as electron-donating, such as alkyl and amino groups. Substitution by electron-withdrawing groups leads, however, only to small changes in barrier heights compared to that of methanediol. A similar tendency was also found for silicon derivatives, but high activation barriers of this reaction remain even for amino group substituted silanediols. Introduction of additional water molecules into the reactive space of carbinol dehydration drastically reduces barrier heights and brings the transition state energy for methanediol close to the experimental value. The difference between dehydration barrier heights for both methanediol and carbinols with electron-rich substituents becomes well-defined for dimeric species. The higher acidity of the hydroxyl group protons in molecules containing halogens and C==O groups brings about a noticeable growth in the dehydration barrier heights of these compounds. This difference in barrier heights for oligomeric species may be the reason for the stability of carbinols with electron-rich substituents.     

Nitrogen/gold codoping of the TiO2(101) anatase surface. A theoretical study based on DFT calculations

The interaction between implanted nitrogen atoms, adsorbed gold atoms, and oxygen vacancies at the anatase TiO(2)(101) surface is investigated by means of periodic density functional theory calculations. Substitutional and interstitial configurations for the N-doping have been considered, as well as several adsorption sites for Au adatoms and different types of vacancies. Our total energy calculations suggest that a synergetic effect takes place between the nitrogen doping on one hand and the adsorption of gold and vacancy formation on the other hand. Thus, while pre-implanted nitrogen increases the adsorption energy for gold and decreases the energy required for the formation of an oxygen vacancy, pre-adsorbed gold or the presence of oxygen vacancies favors the nitrogen doping of anatase. The analysis of the electronic structure and electron densities shows that a charge transfer takes place between implanted-N, adsorbed Au and oxygen vacancies. Moreover, it is predicted that the creation of vacancies on the anatase surface modified with both implanted nitrogen and supported gold atoms produces migration of substitutional N impurities from bulk to surface sites. In any case, the most stable configurations are those where N, Au and vacancies are close to each other.     

Carleson measures for weighted holomorphic Besov spaces

We obtain characterizations of positive Borel measures μ on B ⁿ so that some weighted holomorphic Besov spaces B _s ^p (ω,B ⁿ ) are embedded in L ^p (d μ).     

Pulsed laser deposition of Co and growth of CoSi2 on Si(111)

Monolayers of Co were prepared by pulsed laser deposition (PLD) and thermal deposition (TD) on Si(111) substrates. The surface structure and morphology were studied as a function of annealing temperature with scanning tunneling microscopy and low-energy electron diffraction (LEED). Comparing PLD to TD in the monolayer regime, we find surface phases with lower Co content in the top layer for annealing temperatures below 500 °C, indicating an implantation of Co into the Si substrate. The implanted Co leads to an increased intermixing of Co and Si and a higher density of nucleation centers for Co multilayers produced by PLD compared to TD. Multilayer PLD films therefore show an improved film quality, which is detected by an increased intensity of the LEED reflectivity. PACS 68.37.Ef; 61.14.Hg; 68.55.-a     

A Mixed Heuristic for Circuit Partitioning

As general-purpose parallel computers are increasingly being used to speed up different VLSI applications, the development of parallel algorithms for circuit testing, logic minimization and simulation, HDL-based synthesis, etc. is currently a field of increasing research activity. This paper describes a circuit partitioning algorithm which mixes Simulated Annealing (SA) and Tabu Search (TS) heuristics. The goal of such an algorithm is to obtain a balanced distribution of the target circuit among the processors of the multicomputer allowing a parallel CAD application for Test Pattern Generation to provide good efficiency. The results obtained indicate that the proposed algorithm outperforms both a pure Simulated Annealing and a Tabu Search. Moreover, the usefulness of the algorithm in providing a balanced workload distribution is demonstrated by the efficiency results obtained by a topological partitioning parallel test-pattern generator in which the proposed algorithm has been included. An extented algorithm that works with general graphs to compare our approach with other state of the art algorithms has been also included.     

A Symplectic Slice Theorem

We provide a model for an open invariant neighborhood of any orbit in a symplectic manifold endowed with a canonical proper symmetry. Our results generalize the constructions of Marle and Guillemin and Sternberg for canonical symmetries that have an associated momentum map. In these papers the momentum map played a crucial role in the construction of the tubular model. The present work shows that in the construction of the tubular model, the so-called Chu map, can be used instead, which exists for any canonical action, unlike the momentum map. Hamilton's equations for any invariant Hamiltonian function take on a particularly simple form in these tubular variables. As an application we will find situations, that we will call tubewise Hamiltonian, in which the existence of a standard momentum map in invariant neighborhoods is guaranteed.     

Confining surface state electrons in less than two dimensions: A spectroscopic study

We observe the partial confinement of the twodimensional electron gas of ans-p-like surface state by the regular step distribution of several vicinal Cu(111) surfaces. The spatial distribution of the surface state is visualized by scanning tunneling microscopy. Local tunneling spectroscopy reveals a shift of the maximum of the density of states of the surface state towards the Fermi level, which correlates with the size of the terraces. The average shift is also measured by angle-resolved photoemission and found to be consistent with a one-dimensional Kronig-Penney model.     

Constraints on the time scale of nuclear breakup from thermal hard-photon emission

Measured hard-photon multiplicities from second-chance nucleon-nucleon collisions are used in combination with a kinetic thermal model to estimate the breakup times of excited nuclear systems produced in nucleus-nucleus reactions at intermediate energies. The obtained nuclear breakup time for the ¹²⁹Xe + ^natSn reaction at 50 A MeV is Δτ ≈ 100-300 fm/c for all reaction centralities. The lifetime of the radiating sources produced in seven other different heavy-ion reactions studied by the TAPS experiment is consistent with Δτ ≈ 100 fm/c, such relatively long thermal photon emission times do not seemingly support the interpretation of nuclear breakup as due to a fast spinodal process for the heavy nuclear systems studied.     

Schottky barrier formation in the low metal coverage limit

A theoretical discussion of the state of the art in the field of Schottky barrier formation is presented. The thin metal layer limit is analyzed for Al and In on GaAs(110), and the adsorption sites are determined as a function of the metal coverage. Intrinsic and extrinsic charge neutrality levels are also discussed for the In-case.     

Congruence classes of Frenet curves in complex quadrics

Congruent classes of Frenet curves of order 2 in the complex quadric are studied, obtaining that each congruence class is a level set of a family of certain smooth functions, that are generalizations of isoparametric functions on the unit sphere in the tangent space of the complex quadric.