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Frank Abild-Pedersen Ole Lytken Jakob Engbk Gunver Nielsen Ib Chorkendorff Jens K. Nrskov 《Surface science》2005,590(2-3):127-137
We have, theoretically and experimentally, investigated the dissociation of methane on the terraces and steps of a Ni(1 1 1) surface. Using Density Functional Theory (DFT) total energy calculations combined with Ultra High Vacuum (UHV) experiments, we find that the steps exhibit a higher activity than the terraces. We have, furthermore, investigated how carbon and sulfur present on the surface will deactivate the steps, leaving only the terraces active. We find the intrinsic sticking probabilities of methane on the steps and terraces at 500 K to be 2.8 × 10−7 for the steps and 2.1 × 10−9 for the terraces, in complete agreement with our calculated difference in activation energy of 17 kJ/mol. 相似文献
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Jakob Oren Michaela Vardi Rossana Viskin Sarah Abramson Benzion Fuchs 《Helvetica chimica acta》1993,76(3):1182-1193
The title molecules were shown to photorearrange with remarkable selectivity. Wavelength variation steers the rearrangement modes, of which the [1,2]-acyl shift was found to be largely regioselective, diastereoselective, and enantiospecific. Chemical intercorrelation of products and mechanistic studies were carried out all along. The potential significance of these photochemical processes in selective synthetic schemes is discussed. 相似文献
5.
We give a self‐contained proof of the preservation theorem for proper countable support iterations known as “tools‐preservation”, “Case A” or “first preservation theorem” in the literature. We do not assume that the forcings add reals. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
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Karen Aardal Örjan Jonsson Henrik Jönsson 《The Journal of the Operational Research Society》1989,40(1):65-73
In a practical situation it is often difficult to determine the value of the shortage costs for use in in ventory-control systems. However, in cost-minimization problems including service-level constraints, shortage costs are implicitly prevailing. With the purpose of exploring these relations, a continuous review (Q, r) stock-control system is considered, where the order points and lot sizes are computed simultaneously. Instead of explicitly expressing the shortage cost in the objective function, it is taken into consideration through a service-level constraint. The shadow price of this constraint can in some sense be interpreted as the shortage cost corresponding to the requested service level. By changing the value of the service level, interesting relations between shortage costs and service levels can be viewed for different sets of other inventory parameters. In order to investigate the sensitivity for probabilistic variations in the input data, two different probability distributions are used to describe the lead-time demand. 相似文献
8.
The synthesis of N-methyl-benz[f]isoindole ( 2 ) and N-methyl-dibenz[e,g]isoindole ( 3 ) is reported. The NMR. spectra of N-methyl-isoindole ( 1 ) and of 2 have been analysed and the implications concerning the alternation of bond lengths are discussed. The photophysical properties of 1 to 3 have been investigated by the following methods: HeI photoelectron (PE.) spectroscopy, UV./VIS. absorption (polarization measurements by the stretched-foil technique) and emission spectroscopy (fluorescence spectra, lifetimes and quantum yields, phosphorescence spectra), and flash spectroscopy (triplet-triplet absorption spectra). The discussion of the results is based on HMO. and PPP SCF CI. calculations and points to the relationship between the heterocycles 1 to 3 and the corresponding benzenoid hydrocarbons obtained by replacement of the ? NMe? subunit by ? CH?CH? . Some comments concerning the ground state properties of isoindole and related compounds are derived from the analysis of their electronic structure. 相似文献
9.
Summary The enantioseparation of amphetamine, methamphetamine and various ring-substituted amphetamines by use of a chiral stationary phase carrying immobilized native -cyclodextrin (-CyD) selectors is reported. The system is evaluated for resolving the specified compounds directly without any derivatization and after derivatization with phenyl isothiocyanate (PITC), naphthyl isothiocyanate (NITC) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC). This direct enantioseparation is compared with the features of indirect separation of diasteromeric derivatives after reaction with the optically pure Marfey's reagent employing a simple non-chiral alkyl-silica (RP-8) column. A selection of those methods best suited for each single amphetamine is given.Seventeen different samples of amphetamine, confiscated by the Swedisch police, were analyzed with respect to their enantiomeric composition. Within this set of samples synthesized by the same method no significant deviation from a racemic ratio could be observed. 相似文献
10.
Jakob Wirz 《Helvetica chimica acta》1976,59(5):1647-1655
The HeI photoelectron spectra of the title compound 1 (1,5,9-cyclododecatriene-3,7,11-triyne), 1,5-didehydro[12]annulene (1,3,5,9-cyclododecatetraene-7, 11-diyne ( 2 )), sym-tri-benzotridehydro[12]annulene (tribenzo[a,e,i]-5,6,11,12,17,18-hexadehydrocyclododecene ( 3 )), and sym-dibenzodidehydro[8]annulene (dibenzo[a,e]-5,6,11,12-tetradehydrocyclooctene ( 4 )) have been recorded and analysed on the basis of various semi-empirical model calculations. Despite the distinct bond length alternation in the parent compounds and, apparently, in the radical cations, the first ionization occurs at low energies in these compounds (7.6 ± 0.2 eV). The spectra yield little information with regard to the transannular interactions of the triple bonds. 相似文献