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31.
The C2H2 isothermal dissociation rate on Ni(111) was measured by following, with HREEL spectroscopy, the intensity of the CH stretching peak as a function of time. By repeating the experiment at several different temperatures we have obtained an activation energy of 1.2 ± 0.1 eV/molecule and a pre-exponential factor of 1014±1 s−1 for the first step of the C2H2 dissociation reaction. 相似文献
32.
Costanza Conti Luca Gemignani Lucia Romani 《Advances in Computational Mathematics》2011,35(2-4):217-241
In this paper we describe a general, computationally feasible strategy to deduce a family of interpolatory non-stationary subdivision schemes from a symmetric non-stationary, non-interpolatory one satisfying quite mild assumptions. To achieve this result we extend our previous work (Conti et al., Linear Algebra Appl 431(10):1971?C1987, 2009) to full generality by removing additional assumptions on the input symbols. For the so obtained interpolatory schemes we prove that they are capable of reproducing the same space of exponential polynomials as the one generated by the original approximating scheme. Moreover, we specialize the computational methods for the case of symbols obtained by shifted non-stationary affine combinations of exponential B-splines, that are at the basis of most non-stationary subdivision schemes. In this case we find that the associated family of interpolatory symbols can be determined to satisfy a suitable set of generalized interpolating conditions at the set of the zeros (with reversed signs) of the input symbol. Finally, we discuss some computational examples by showing that the proposed approach can yield novel smooth non-stationary interpolatory subdivision schemes possessing very interesting reproduction properties. 相似文献
33.
Metal derivatives of the octacationic tetrakis-2,3-[5,6-di{2-(N-methyl)pyridiniumyl}pyrazino]porphyrazine macrocycle [(2-Mepy)(8)TPyzPzH(2)](8+) (2-Mepy = 2-(N-methyl)pyridiniumyl ring) isolated as water-soluble hydrated iodide salts of the general formula [(2-Mepy)(8)TPyzPzM](I(8)).xH(2)O, (M = Mg(II)(H(2)O), Co(II), Cu(II), Zn(II); x = 2-5) were prepared from the corresponding neutral complexes [Py(8)TPyzPzM].xH(2)O previously reported. Reaction of these complexes with CH(3)I in N,N-dimethylformamide under mild conditions led to full quaternization of all eight pyridine N atoms and formation of the octacations [(2-Mepy)(8)TPyzPzM](8+). Clathrated water molecules could be eliminated from the species [(2-Mepy)(8)TPyzPzM](I(8)).xH(2)O by mild heating ( Co(I) process, but the site of electron transfer is reversed and the final product upon a further one-electron reduction is formulated as a Co(II) dianion as opposed to a Co(I) pi-anion radical. This sequence is similar to what was earlier reported for reduction of the same compound in pyridine. Reversible one-electron oxidations are also observed for the unmethylated species [Py(8)TPyzPzM].xH(2)O where M = Co(II) and Mn(II) in DMSO. Remarkably, the octacationic macrocycles [(2-Mepy)(8)TPyzPzM](I(8)).xH(2)O, (M = Mg(II)(H(2)O), Co(II), Cu(II), and Zn(II); x = 2-5) are more easily reduced at any step of the reduction than the corresponding unquaternized species with the same metal ion. This indicates a higher tendency to stepwise electron uptake after the quaternization process, which enhances the charge redistribution capability within the species formed by the electroreduction. 相似文献
34.
Costanza Conti Mariantonia Cotronei 《Journal of Computational and Applied Mathematics》2010,233(7):1649-1659
In this extension of earlier work, we point out several ways how a multiresolution analysis can be derived from a finitely supported interpolatory matrix mask which has a positive definite symbol on the unit circle except at −1. A major tool in this investigation will be subdivision schemes that are obtained by using convolution or correlation operations based on replacing the usual matrix multiplications by Kronecker products. 相似文献
35.
Optimal control problems for bilinear systems are studied and solved with a view to approximating analogous problems for general nonlinear systems. For a given bilinear optimal control problem, a sequence of linear problems is constructed, and their solutions are shown to converge to the desired solution. Also, the direct solution to the Hamilton-Jacobi equation is analyzed. A power-series approach is presented which requires offline calculations as in the linear case (Riccati equation). The methods are compared and illustrated. Relations to classical linear systems theory are discussed. 相似文献
36.
Cédric Sarazin Nathalie Delaunay Anne Varenne Christine Costanza Véronique Eudes Pierre Gareil 《Journal of separation science》2010,33(20):3177-3183
Bursts resulting from the chemical reaction between hydrochloric or nitric acid with aluminum foils are very often committed by the young delinquency in western countries because of its easiness of achievement. A fast, simple, selective, and cost‐effective method allowing the simultaneous detection of chloride and nitrate anions and aluminum(III) was thus required. This article focused on the development and validation of a CE method using a BGE containing 2,6‐pyridinedicarboxylic acid (PDC) acting as both an anionic chromophore and as an aluminum(III) complexing agent. First, the achievement of the speciation diagram of Al(III) in the presence of PDC allowed the choice of pH conditions for which aluminum(III) was globally anionic. The study of the selectivity for Al(III) in the presence of ten other cationic species potentially present in post‐blast residues dictated the choice of the PDC concentration at 20 mM. The validation step next demonstrated the figures of merit of the method, with an intermediate precision for Al(III) of 2% on normalized migration times and 3.5% on corrected areas. Finally, this method was used for analyses of real post‐blast extracts from acid–aluminum mixtures. 相似文献
37.
38.
Rosi F Burnstock A Van den Berg KJ Miliani C Brunetti BG Sgamellotti A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2009,71(5):1655-1662
The palette used in two paintings by Paul Cézanne, L'étang des soeurs dated c. 1875 and La route tournante, made in the last year of his life (1902), were analyzed using non-invasive spectroscopic methods. X-ray fluorescence combined with principal components analysis (PCA) and supported by reflectance near- and mid-FTIR was shown to be a powerful analytical tool to draw conclusions about the chemical identification of inorganic materials in paintings. Pigments and fillers such us Thénard's blue, Prussian blue, red ochre, kaolin, vermilion, lead white, zinc white and barium sulphate, were identified. Evidence for three different pigments, namely a copper arsenite pigment, chrome green (a mixture of chrome yellow and Prussian blue) and viridian has been obtained by the PCA analysis of elemental compositions of green hues. 相似文献
39.
van den Belt M Bianciotto OA Costanza R Demers S Diaz S Ferreyra GA Koch EW Momo FR Vernet M 《Photochemistry and photobiology》2006,82(4):865-877
This article describes the use of group model building to facilitate interaction with stakeholders, synthesize research results and assist in the development of hypotheses about climate change at the global level in relation to UV-B radiation and ecosystem service valuation. The objective was to provide a platform for integration of the various research components within a multidisciplinary research project as a basis for interaction with stakeholders with backgrounds in areas other than science. An integrated summary of the scientific findings, along with stakeholder input, was intended to produce a bridge between science and policymaking. We used a mediated modeling approach that was implemented as a pilot project in Ushuaia, Argentina. The investigation was divided into two participatory workshops: data gathering and model evaluation. Scientists and the local stakeholders supported the valuation of ecosystem services as a useful common denominator for integrating the various scientific results. The concept of economic impacts in aquatic and marsh systems was represented by values for ecosystem services altered by UV-B radiation. In addition, direct local socioeconomic impacts of enhanced UV-B radiation were modeled, using data from Ushuaia. We worked with 5 global latitudinal regions, focusing on net primary production and biomass for the marine system and on 3 plant species for the marsh system. Ecosystem service values were calculated for both sectors. The synthesis model reflects the conclusions from the literature and from experimental research at the global level. UV-B is not a significant stress for the marshes, relative to the potential impact of increases in the sea level. Enhanced UV-B favors microbial dynamics in marine systems that could cause a significant shift from primary producers to bacteria at the community level. In addition, synergetic effects of UV-B and certain pollutants potentiate the shift to heterotrophs. This may impact the oceanic carbon cycle by increasing the ratio of respiratory to photosynthetic organisms in surface waters and, thus, the role of the ocean as a carbon sink for atmospheric CO2. In summary, although changes in the marine sector due to anthropogenic influences may affect global climate change, marshes are expected to primarily be affected by climate change. 相似文献
40.
The exact formulation of the kinetic of dimer in hypercubic lattices is developed in the framework of the kinetic lattice gas model. The so-called local evolution rules are used to obtain the hierarchy of equation of motion for the correlation functions where processes like adsorption and desorption are included. The hierarchy of equations are truncated using a mean field (m, n) closures which allows the analytical treatment of the system. A general expression for non-interacting dimer isotherm and two particle correlation functions are obtained in hypercubic lattices. 相似文献