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21.
Model complexes of hexaethynylhexamethoxy[6]pericyclyne (HM6P) molecules, with or without dichloromethane (DCM) guests, have been calculated at the M05-2X/6-311G(d,p) DFT level. Analysis of nonbonding interactions shows that the cohesion of the supramolecular tubular assemblies previously observed in the crystal state, relies mainly on C-H···O hydrogen bonds between axial ethynyl and equatorial methoxy substituents of stacked HM6P C(18) macrocycles in a cyclohexane-like chair conformation. The intrinsic binding energy of one HM6P molecule with two neighbors is calculated to be more than 40 kcal mol(-1). The inner channel of the stacks (of ca. 8 ? diameter) are suitable for hosting DCM molecules. Using the Atoms In Molecules (AIM) theory, the interaction between DCM molecules and surrounding triple bonds is analyzed in terms of σ-hole-directed C-Cl···π halogen bonds. A σ-hole-directed Cl···Cl interaction between two chlorine atoms of different DCM molecules is also evidenced.  相似文献   
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A 100-kW three-phase ac plasma furnace with sheathed copper electrodes (sheathing gas: air) is presented. It is used for spheroidizing chamotte (refractory-fired clay) particles having a smooth, pore-free surface. A simple, one-dimensional numerical model for the heat transfer to the particles explains the maximum processing rate and the detrimental influence of an inhomogeneous particle size distribution.  相似文献   
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The beta decay rate of the16N(0?; 120keV) →16O(0+, G.S.) transition has been remeasured. Our result (Λ β =0.48±0.024 s?1) is in excellent agreement with a previous measurement but strongly disagrees with another experimental value. The two agreeing results provide an experimental verification of the importance of meson exchange currents in 0+-0? weak transitions. A value ofg p/g A~11–12 can be inferred from the correspondingΛ μ rate.  相似文献   
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Angular distributions for polarized proton inelastic scattering cross sections along with the analysing power for the reaction 16O(p, p′)16O1(2?, 8.88 MeV) at Ep=42.5, 44.0 and 49.3 MeV have been measured. A semidirect reaction analysis augments the evidence for octupole giant resonance strength in the 30 to 50 MeV energy region.  相似文献   
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A phase-shift analysis of combined cross-section and spin-correlation data has been performed for the elastic scattering of protons by deuterons. Reliable doublet phases have been extracted and compared with extensive Faddeev-type calculations using different rank-one separable interactions. The effect of P-wave N-N forces is discussed and intrinsic strengths and range are deduced.  相似文献   
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Three heterotetranuclear complexes, [{Ru(II)(bpy)(2)(L(n))}(3)Mn(II)](8+) (bpy = 2,2'-bipyridine, n = 2, 4, 6), in which a Mn(II)-tris-bipyridine-like centre is covalently linked to three Ru(II)-tris-bipyridine-like moieties using bridging bis-bipyridine L(n) ligands, have been synthesised and characterised. The electrochemical, photophysical and photochemical properties of these complexes have been investigated in CH(3)CN. The cyclic voltammograms of the three complexes exhibit two successive very close one-electron metal-centred oxidation processes in the positive potential region. The first, which is irreversible, corresponds to the Mn(II)/Mn(III) redox system (E(pa) approximately 0.82 V vs Ag/Ag(+) 0.01 M in CH(3)CN-0.1 M Bu(4)NClO(4)), whereas the second which is, reversible, is associated with the Ru(II)/Ru(III) redox couple (E(1/2) approximately 0.91 V). In the negative potential region, three successive reversible four electron systems are observed, corresponding to ligand-based reduction processes. The three stable dimeric oxidized forms of the complexes, [Mn(2)(III,IV)O(2){Ru(II)(bpy)(2)(L(n))}(4)](11+), [Mn(2)(IV,IV)O(2){Ru(II)(bpy)(2)(L(n))}(4)](12+) and [Mn(2)(IV,IV)O(2){Ru(III)(bpy)(2)(L(n))}(4)](16+) are obtained in fairly good yields by sequential electrolyses after consumption of respectively 1.5, 0.5 and 3 electrons per molecule of initial tetranuclear complexes. The formation of the di-micro-oxo binuclear complexes are the result of the instability of the {[Ru(II)(bpy)(2)(L(n))](3)Mn(III)}(9+) species, which react with residual water, via a disproportionation reaction and the release of one ligand, [Ru(II)(bpy)(2)(L(n))](2+). A quantitative yield can be obtained for these reactions if the electrochemical oxidations are performed in the presence of an added external base like 2,6-dimethylpyridine. Photophysical properties of these compounds have been investigated showing that the luminescence of the Ru(II)-tris-bipyridine-like moieties is little affected by the presence of manganese within the tetranuclear complexes. A slight quenching of the excited states of the ruthenium moieties, which occurs by an intramolecular process, has been observed. Measurements made at low concentration (<1 x 10(-5) M) indicate that some decoordination of Mn(2+) arises in 1a-c. These measurements allow the calculation of the association constants for these complexes. Finally, photoinduced oxidation of the tetranuclear complexes has been performed by continuous photolysis experiments in the presence of a large excess of a diazonium salt, acting as a sacrificial oxidant. The three successive oxidation processes, Mn(II)--> Mn(III)Mn(IV), Mn(III)Mn(IV)--> Mn(IV)Mn(IV) and Ru(II)--> Ru(III) are thus obtained, the addition of 2,6-dimethylpyridine in the medium giving an essentially quantitative yield for the two first photo-induced oxidation steps as found for electrochemical oxidation.  相似文献   
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We have measured the effect of microwave irradiation on the dc current-voltage characteristics of superconducting atomic contacts. The interaction of the external field with the ac supercurrents leads to replicas of the supercurrent peak, the well-known Shapiro resonances. The observation of supplementary fractional resonances for contacts containing highly transmitting conduction channels reveals their nonsinusoidal current-phase relation. The resonances sit on a background current which is itself deeply modified, as a result of photon-assisted multiple Andreev reflections. The results provide firm support for the full quantum theory of transport between two superconductors based on the concept of Andreev bound states.  相似文献   
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