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31.
Decleva P Fronzoni G Stener M de Simone M Coreno M Green JC Hazari N Plekan O 《Physical review letters》2005,95(26):263401
Photoemission from the two outermost ionizations [highest occupied molecular orbitals (HOMO and HOMO-1)] of Mg(eta(5)-C(5)H(5))(2) has been studied with synchrotron radiation in the gas phase. Strong oscillations in the HOMO-1/HOMO ratio, qualitatively similar to those well-known for fullerenes, are found. Excellent agreement with the experimental ratio is provided by accurate cross section calculations both at the density-functional theory and time-dependent density-functional theory level, indicating that a many electron response has a minor role for this effect. A comparison with the calculated values for other metal sandwich compounds indicate that the presence of oscillations is a widespread phenomenon, and a potential source of interesting information on the structural and electronic properties of the target molecule. 相似文献
32.
33.
An open volume, high isolation, radio frequency surface coil system for pulsed magnetic resonance 总被引:1,自引:1,他引:0
Curto CA Placidi G Sotgiu A Alecci M 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):353-358
We present an open volume, high isolation, RF system suitable for pulsed NMR and EPR spectrometers with reduced dead time. It comprises a set of three RF surface coils disposed with mutually parallel RF fields and a double-channel receiver (RX). Theoretical and experimental results obtained with a prototype operating at about 100 MHz are reported. Each surface RF coil (diameter 5.5 cm) was tuned to f0 = 100.00 ± 0.01 MHz when isolated. Because of the mutual coupling and the geometry of the RF coils, only two resonances at f1 = 97.94 MHz and f2 = 101.85 MHz were observed. We show they are associated with two different RF field spatial distributions. In continuous mode (CW) operation the isolation between the TX coil and one of the RX coils (single-channel) was about −10 dB. By setting the double-channel RF assembly in subtraction mode the isolation values at f1 or f2 could be optimised to about −75 dB. Following a TX RF pulse (5 μs duration) an exponential decay with time constant of about 600 ns was observed. The isolation with single-channel RX coil was about −11 dB and it increased to about −47 dB with the double-channel RX in subtraction mode. Similar results were obtained with the RF pulse frequency selected to f2 and also with shorter (500 ns) RF pulses. The above geometrical parameters and operating frequency of the RF assembly were selected as a model for potential applications in solid state NMR and in free radical EPR spectroscopy and imaging. 相似文献
34.
Bianco A Guiso M Ballero M Foddai S Nicoletti M Piccin A Serafini M Tomassini L 《Natural product research》2004,18(3):241-246
During our systematic study on the species of genus Linaria (Scrophulariaceae) present in Italy, we examined the glycosidic fraction of Linaria capraria Moris et De Not., a species endemic of Tuscany archipelago. This fraction is particularly complex and we considered in this article only the medium polarity components. In accordance with previous studies, L. capraria shows acyl derivatives of antirrhinoside 1 as specific chemotaxonomic iridoidic markers. L. capraria exhibits a complex composition, with regard to iridoidic constituents, with several chromatographic problems to be resolved. We then isolated, besides the known antirrhinoside 1, two acyl derivatives of antirrhinoside, the 6'-O-senecioyl derivative, 2, and the 6'-O-angeloyl derivative, 3. In addition a glucoside of an acyclic monoterpene, 4, was also isolated, which may be correlated to the other monoterpenic glycosides isolated from other species of Scrophulariaceae. 相似文献
35.
36.
Pietro Franceschi Roland Thissen Odile Dutuit Christian Alcaraz Heloise Soldi-Lose Davide Bassi Daniela Ascenzi Paolo Tosi Jan Zabka Zdenek Herman Marcello Coreno Monica de Simone 《International journal of mass spectrometry》2009,280(1-3):119
The long-lived excited states of doubly charged rare gases can markedly affect their reactivity. In this paper we demonstrate the presence of strong state-specific effects in the charge exchange of Ar2+ (3P, 1D and 1S) with several neutral targets (He, Ne, Kr, Xe, D2, and CH4). State sensitive measurements have been performed by producing the different Ar2+ electronic states via tunable synchrotron radiation (Elettra-Trieste, Italy and SuperACO-Orsay, France). From the product ion yield data of charge transfer, state-selected total cross-sections have been deduced. Using the state-specific reactivity of Ar2+ towards different neutral targets, it has been possible to extract the photon-energy-dependent production branching of the three doubly charged states and to investigate the autoionization dynamics of neutral or singly charged Ar in the vicinity of the double ionization threshold. 相似文献
37.
For Principal Component Analysis in Reproducing Kernel Hilbert Spaces (KPCA), optimization over sets containing only linear
combinations of all n-tuples of kernel functions is investigated, where n is a positive integer smaller than the number of data. Upper bounds on the accuracy in approximating the optimal solution,
achievable without restrictions on the number of kernel functions, are derived. The rates of decrease of the upper bounds
for increasing number n of kernel functions are given by the summation of two terms, one proportional to n
−1/2 and the other to n
−1, and depend on the maximum eigenvalue of the Gram matrix of the kernel with respect to the data. Primal and dual formulations
of KPCA are considered. The estimates provide insights into the effectiveness of sparse KPCA techniques, aimed at reducing
the computational costs of expansions in terms of kernel units. 相似文献
38.
Constitutive branching analysis of cylindrical bodies under in-plane equibiaxial dead-load tractions
Finite homogeneous deformations of hyperelastic cylindrical bodies subjected to in-plane equibiaxial dead-load tractions are analyzed. Four basic equilibrium problems are formulated considering incompressible and compressible isotropic bodies under plane stress and plane deformation condition. Depending on the form of the stored energy function, these plane problems, in addition to the obvious symmetric solutions, may admit asymmetric solutions. In other words, the body may assume an equilibrium configuration characterized by two unequal in-plane principal stretches corresponding to equal external forces. In this paper, a mathematical condition, in terms of the principal invariants, governing the global development of the asymmetric deformation branches is obtained and examined in detail with regard to different choices of the stored energy function. Moreover, explicit expressions for evaluating critical loads and bifurcation points are derived. With reference to neo-Hookean, Mooney-Rivlin and Ogden-Ball materials, a broad numerical analysis is performed and the qualitatively more interesting asymmetric equilibrium branches are shown. Finally, using the energy criterion, a number of considerations are put forward about the stability of the computed solutions. 相似文献
39.
Silvia Sternativo Francesca Del Verme Antonella Calandriello Lorenzo Testaferri Marcello Tiecco 《Tetrahedron》2010,66(34):6851-9385
Variously substituted aziridines were conveniently prepared by an aza-Michael Initiated Ring Closure (aza-MIRC) reaction starting from vinyl selenones and primary amines, aminoalcohols or diamines. The reactions proceed in very high yields at room temperature in toluene or water. A significant rate acceleration was observed under aqueous conditions. 相似文献
40.
Three new N2S2 donor ligands 1,1′-((2-(2-(phenylthio)phenylthio)phenyl)methylene)bis(3,5-R-1H-pyrazole), R = H (LH), R = Me (LMe), R = i-Pr (Li-Pr) have been prepared and characterized. These bifunctional ligands incorporate two distinct chelate donor systems, by virtue of the presence of bispyrazole and bisthioether functions. The preferred conformation of these ligands is such that the N2 and S2 donor moieties may be oriented in opposite directions, thus favoring the formation of molecular chains when treated with AgBF4. The X-ray structures of Ag(I) complexes show that, depending on the steric hindrance present on the pyrazole rings, these ligands behave as κ4-SSNN-μ bridging tetradentate (when R = H), or κ3-SNN-μ bridging tridentate (when R = Me, i-Pr). Interestingly, [Ag(LH)]BF4 crystallizes in the chiral space group P41, with the molecular chain that is folded around the 41 screw axis. 相似文献