CLUSTER LEED - A VERY FAST METHOD FOR SURFACE-STRUCTURE DETERMINATION

A very fast method, cluster low-energy electron diffraction (LEED) is proposed for LEED I-V spectral analysis, in which three appproximations are introduced: the small-atom approximation, omission of the structure factors, and truncation of higher order ( > 2) scattering events. The method has been tested using a total of four sets of I-V spectra calculated by fully dynamic LEED for (i) the simple overlayer system, O on Ni{100}, and (ii) the reconstructed system, Cu on W{100}, and also one set of experimental data from W{100}-c(2 X 2)-Cu. In each case the correct structural parameters are recovered. It is suggested that for complex systems cluster LEED provides an efficient fast route to trial structures, which could be refined by automated tenser LEED.

VIEWING LEED PATTERNS AS ELECTRON HOLOGRAMS

It is shown theoretically that LEED patterns from ordered overlayer systems bear a strong relationship to electron holograms, and that phase information is recorded in the diffraction intensities. It is, therefore, possible to obtain structural information by direct holographic inversion from conventional LEED I-V spectra.

A DIRECT INVERSION METHOD FOR SURFACE-STRUCTURE DETERMINATION FROM LEED INTENSITIES

LOW-ENERGY electron diffraction (LEED) has become the most successful technique in surface crystallography1, but because of the complexity of the surface-electron scattering interactions, analyses of LEED data are still conducted on a trial-and-error basis: a direct-inversion method for treating LEED intensity data remains an attractive goal2. Building on recent theoretical and experimental developments in electron holography from surface structures3-16, we show here that three-dimensional images with atomic resolution can be obtained by a direct transform of conventional LEED intensity spectra.

A LEED STRUCTURAL STUDY OF THE CO INDUCED RECONSTRUCTION OF PD(110) - EVIDENCE FOR A MISSING ROW STRUCTURE

Molecularly adsorbed CO on Pd{110} has been shown (R. Raval et al., Chem. Phys. Lett. 167 (1990) 391, ref. [1]) to induce a substantial reconstruction of the surface in the coverage range 0.3 <theta less-than-or-equal-to 0.75. Throughout this coverage range, the adsorbate-covered reconstructed surface exhibits a (4 x 2) LEED pattern. However, the exact nature of the reconstruction remains uncertain. We have conducted a LEED I(E) "fingerprinting" analysis of the CO/Pd{110}-(4 x 2) structure in order to establish the type of reconstruction induced in the metal surface. This study shows that the LEED I(E) profiles of the integral order and appropriate half-order beams of the CO/Pd{110}-(4 x 2) pattern closely resemble the I(E) profiles theoretically calculated for a Pd{110}-(1 x 2) missing-row structure. Additionally, there is a strong resemblance to the experimental LEED I(E) profiles for the Cs/Pd{110}-(1 x 2) structure which has also been shown to exhibit the missing-row structure. On the basis of this evidence we conclude that the CO/Pd{110}-(4 x 2) LEED pattern arises from a missing-row reconstruction of the Pd{110} surface which gives rise to a strong underlying (1 x 2) pattern plus a poorly ordered CO overlayer which produces weak, diffuse fourth-order spots in the LEED pattern.

Confronto tra diverse localizzazioni di un impianto eolico contemperando produttività ed impatto visivo

This paper proposes a series of variations in designing the location of a wind farm on Monti della Tolfa. These project solutions aim at mitigating the visual impact caused by the wind aerogenerators. Besides the usual location of the wind aerogenerators on the skyline, these alternatives within the project design relate to the placement of wind turbines in the middle and at the bottom of the hillside. Other possible mitigation forms relate to the dimensions and the colour of the wind towers. This study proposes both a non-monetary and monetary analysis of the visual impact related to each project proposal. The final aim of the paper is to analyze economic and financial costs-benefits for each alternative to find out the economic optimal solution.

Structural and electronic properties of Ce overlayers and low-dimensional Pt-Ce alloys on Pt{111}

The structural, thermal, chemisorptive, and electronic properties of Ce on Pt{111} are studied by photoemission, Auger spectroscopy, scanning tunnel microscope (STM), and low-energy electron diffraction (LEED). Stranski-Krastanov-like growth of low-density Ce layers is accompanied by substantial valence charge transfer from Ce to Pt: in line with this, the measured dipole moment and polarizability of adsorbed Ce at low coverages are 7.2 x 10(-30) C m and similar to 1.3x10(-29) m(3), respectively. Pt-Ce intermixing commences at similar to 400 K and with increasing temperature a sequence of five different ordered surface alloys evolves. The symmetry, periodicities, and rotational epitaxy observed by LEED are in good accord with the STM data which reveal the true complexity of the system. The Various bimetallic surface phases are based on growth of crystalline Pt5Ce, a hexagonal layer structure consisting of alternating layers of Pt2Ce and Kagome nets of Pt atoms. This characteristic ABAB layered arrangement of the surface alloys is clearly imaged, and chemisorption data permit a distinction to be made between the more reactive Pt2Ce layer and the less reactive Pt Kagome net. Either type of layer can appear at the surface as the terminating structure, thicker films exhibiting unit mesh parameters characteristic of the bulk alloy.

Ensemble effects in the coupling of acetylene to benzene on a bimetallic surface: A study with Pd{111}/Au

Acetylene coupling to benzene on the Pd(lll) surface is greatly enhanced by the presence of catalytically inert Au atoms. LEED and Auger spectroscopy show that progressive annealing of Au overlayers on Pd(lll) leads to the formation of a series of random surface alloys with continuously varying composition. Cyclization activity is a strong function of surface composition-the most efficient catalyst corresponds to a surface of composition similar to 85% Pd. CO TPD and HREELS data show that acetylene cyclization activity is not correlated with the availability of singleton Pd atoms, nor just with the presence of 3-fold pure Pd sites-the preferred chemisorption site for C2H2 on Pd{111}. The data can be quantitatively rationalized in terms of a simple model in which catalytic activity is dominated by Pd6Au and Pd-7 surface ensembles, allowance being made for the known degree to which pure Pd{111} decomposes the reactant and product molecules.

Electro-oxidation of CO at the Ru(0001) single-crystal electrode surface

In situ FTIR spectroscopic and electrochemical data and ex situ (emersion) electron diffraction (LEED) and RHEED) and Auger spectroscopic data are presented on the structure and reactivity, with respect to the electro-oxidation of CO, of the Ru(0001) single-crystal surface in perchloric acid solution. In both the absence and the presence of adsorbed CO, the Ru(0001) electrode shows the potential-dependent formation of well-defined and ordered oxygen-containing adlayers. At low potentials (e.g., from -80 to +200 mV vs Ag/AgCl), a (2 × 2)-O phase, which is unreactive toward CO oxidation, is formed, in agreement with UHV studies. Increasing the potential results in the formation of (3 × 1) and (1 × 1) phases at 410 and 1100 mV, respectively, with a concomitant increase in the reactivity of the surface toward CO oxidation. Both linear (CO ) and three-fold-hollow (CO ) binding CO adsorbates (bands at 2000-2040 and 1770-1800 cm , respectively) were observed on the Ru(0001) electrode. The in situ FTIR data show that the adsorbed CO species remain in compact islands as CO oxidation proceeds, suggesting that the oxidation occurs at the boundaries between the CO and O domains. At low CO coverages, reversible relaxation (at lower potentials) and compression (at higher potentials) of the CO adlayer were observed and rationalized in terms of the reduction and formation of surface O adlayers. The data obtained from the Ru(0001) electrode are in marked contrast to those observed on polycrystalline Ru, where only linear CO is observed.

Identification of the structure of a CO adlayer on a Pt(111) electrode

The structure of a Pt(111) electrode after treatment in an electrolyte and subsequent transfer to an UHV chamber was investigated ex situ by combined low energy electron diffraction (LEED), reflection high energy electron diffraction (RHEED), and Auger electron spectroscopy (AES). Treatment of the sample in a CO saturated 0.1 M HClO solution at potentials between -0.2 and 0.2 V versus Ag/AgCl caused a maximum CO coverage of about 0.75 as probed by cyclic voltammetry, which dropped by partial desorption to about 0.25 upon transfer to the UHV chamber. This adlayer exhibited a (distorted) 3×3 R30° pattern by RHEED (but not with LEED) exhibiting an average domain size of 2.3 nm at room temperature. This is identified with the same phase reported before from gas phase studies, as also corroborated by the similarities of the vibrational spectroscopic data. The same structure (albeit even more poorly ordered) was found after dissociative adsorption of methanol.

Il performance measurement negli enti locali. Strumenti innovativi nella prospettiva economico-aziendale

In un'epoca di risorse scarse e di crescente disaffezione verso la politica, l'azione degli enti locali ha un impatto sempre più rilevante sulla qualità della vita del cittadino. A tal fine, l'adozione di sistemi di programmazione e controllo, supportati da idonei strumenti, diviene essenziale per il perseguimento dell'efficienza e dell'efficacia e dunque per riconquistare la fiducia del cittadino stesso. Il volume, sulla base di un'analisi della normativa (dai primi anni Novanta fino al DL 174/2012 e s.m.i.) e della letteratura nazionale ed internazionale in tema di performance measurement, identifica un Modello ottimale (Modello PerformEL) per la redazione di due documenti che possono avere un ruolo centrale nel sistema di programmazione e controllo locale: il Piano e la Relazione sulla Performance. La capacità informativa di questi ultimi è testata tramite un'indagine empirica che ha coinvolto i comuni con almeno 50.000 abitanti, comparando struttura, forma e contenuti di tali documenti con quelli ritenuti ottimali e quindi inseriti nel Modello. Sulla base dei risultati dell'indagine, che mostrano una diffusa inadeguatezza informativa degli strumenti analizzati, viene proposto un percorso evolutivo per la graduale realizzazione di documenti di programmazione e controllo che, al di là della loro 'etichetta formale' (Piano della Performance piuttosto che Piano Esecutivo di Gestione, Relazione sulla Performance o Report dei Controlli interni) permetta di semplificare l'architettura informativa dell'ente locale (nel rispetto del DL 174/2012) e parimenti di trasformare i molteplici inutili adempimenti in utili documenti di performance measurement.

Programmazione e controllo dei gruppi pubblici locali. Dagli strumenti esistenti alle soluzioni innovative per la governance.

Il tema dei servizi pubblici locali è sicuramente centrale nell'attuale contesto socio-economico nazionale ed internazionale, in quanto essi hanno un impatto determinante sulle condizioni di vita dei cittadini e sulla competitività dei sistemi economici. In ragione di ciò, negli ultimi anni in Italia numerose riforme si sono susseguite, con lo scopo di individuare l'assetto più efficace ed efficiente per tale settore. Le suddette riforme hanno così ridisegnato il ruolo degli Enti Locali, che saranno sempre meno gestori diretti e sempre più direttori di una multiforme orchestra composta dalle aziende esterne chiamate a fornire in prima persona le prestazioni agli utenti finali. Il presente lavoro si propone di individuare, anche attraverso una ricerca sui Comuni capoluogo di Emilia-Romagna e Toscana, strumenti di programmazione e controllo in ottica di gruppo che consentano agli Enti Locali di svolgere questo nuovo delicato ruolo. Tali strumenti verranno disegnati sulla base delle necessità informative delle amministrazioni indagate e nel rispetto delle più recenti riforme in tema di programmazione, rilevazione, gestione, controllo, valutazione e comunicazione delle performance pubbliche.

Density functional theory study of the interaction between CO and on a Pt surface:CO/Pt(111), O/Pt(111), and CO/O/Pt(111)

Ab initio total energy calculations within the Density Functional Theory framework were carried out for Pt(111), Pt(111)-p(2x2)-CO, Pt(111)-p(2x2)-O, and Pt(111)-p(2x2)-(CO+O) to provide an insight into the interaction between CO and O on metal surfaces, an important issue in CO oxidation, and also in promotion and poisoning effects of catalysis. The geometrical structures of these systems were optimized with respect to the total energy, the results of which agree with existing experimental values very well. It is found that (i) the local structures of Pt(111)-p(2x2)-(CO+O), such as the bond lengths of C-O, C-Pt, and O-Pt (chemisorbed O atom with Pt), are almost the same as that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively, (ii) the total valence charge density distributions in Pt(111)-p(2x2)-(CO+O) are very similar to that in Pt(111)-p(2x2)-CO, except in the region of the chemisorbed oxygen atom, and also nearly identical to that in Pt(111)-p(2x2)-O, apart from in the region of the chemisorbed CO, and (iii) the chemisorption energy of CO on a precovered Pt(111)-p(2x2)-O and the chemisorption energy of O on a precovered Pt(111)-p(2x2)CO are almost equal to that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively. These results indicate that the interaction between CO and chemisorbed oxygen on a metal surface is mainly shore range in nature. The discussions of Pt-CO and Pt-O bonding and the interaction between CO and the chemisorbed oxygen atom on Pt(111) are augmented by local densities of states and real space distributions of quantum states.