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21.
In this work the spectrum of the water molecule has been the subject of extensive experimental and theoretical investigations. More than 1500 transitions have been assigned in a far infrared emission spectrum recorded in the 50-500 cm−1 region and experimental rotational energies have been obtained for the second triad of interacting states, (0 3 0), (1 1 0), and (0 1 1), up to J=10 using flame spectroscopy. These new data along with a large data set of already published experimental rotational energies, high-resolution infrared transitions, and microwave lines, involving the eight first vibrational states, have been analyzed using the theoretical formalism developed for water in a previous paper (J. Mol. Spectrosc. 206 (2001) 83), which accounts for the anomalous centrifugal distortion as well as for the Fermi- and Coriolis-type couplings. 相似文献
22.
Phenomena Involved in Suspension Plasma Spraying Part 2: Zirconia Particle Treatment and Coating Formation 总被引:1,自引:0,他引:1
C. Delbos J. Fazilleau V. Rat J. F. Coudert P. Fauchais B. Pateyron 《Plasma Chemistry and Plasma Processing》2006,26(4):393-414
The first part of this paper was devoted to phenomena related to liquid injection in the Suspension Plasma Spraying (SPS) process. This second part emphasizes the solid particles treatment and the coating generation. A simplified theoretical approach is proposed to evaluate the influence of the numerous experimental parameters on heat and momentum transfers from the plasma jet to individual particles. It is shown that small solid particles vanish by vaporization and are very sensitive to plasma arc fluctuations and thermophoresis effect, which makes particles to escape from the jet. This study is completed by experimental investigations concerning, first, in-flight collection of particles and, second, coating elaboration. The importance of the particle size distribution of the injected powder and the parameters for the plasma generation is demonstrated, as their choice can give either porous or dense coatings. 相似文献
23.
24.
The millimeter wave spectrum of the Ar-CHF3 complex is measured. The microwave lines are split into two components due to tunneling between three equivalent minima. Aided by ab initio calculations, the bidimensional potential energy surface of the complex is investigated and the rotational dependence of the tunneling splitting is parameterized using an IAM-like approach. The analysis of the microwave data allows us to determine the parameters involved in this rotational dependence. The value obtained are consistent with a large amplitude motion involving a 2π/3 internal rotation of the CHF3 moiety about its threefold axis of symmetry. Information about the geometry of the intermediate configuration of this large amplitude motions is obtained. 相似文献
25.
26.
Mousset D Gillaizeau I Sabatié A Bouyssou P Coudert G 《The Journal of organic chemistry》2006,71(16):5993-5999
Symmetrical and unsymmetrical 2,6-disubstituted dihydropyridines were prepared in high yields under mild conditions using the Suzuki and Stille Pd-catalyzed coupling reactions of imide-derived bisvinyl phosphates with a range of aryl, heteroaryl, and alkenyl moieties. The alkylation reaction at C-4 easily afforded original tri- and tetrasubstituted dihydropyridines. Hydrolysis of the latter under acidic condition provided efficiently either open-chain 1,5-diketones or di- or trisubstituted pyridines. 相似文献
27.
It has been proved that the “complex base” NaNH2-t-BuONa is capable of performing syn-eliminations with compounds of the cyclohexane series, particularly with trans 1,2-dibromocyclohexanes. The equatorial position of the halogen favours such a reaction. A cyclic mechanism (of the Sicher-Zavada type) is proposed. The same reactions have been carried out in the cyclopentane and cycloheptane series. In these two cases an E2H-mechanism seems more probable. 相似文献
28.
J. F. Brilhac B. Pateyron J. F. Coudert P. Fauchais A. Bouvier 《Plasma Chemistry and Plasma Processing》1995,15(2):257-277
This work was devoted to the study of the dynamic and static behavior of de vortex plasma torch with a well-type cathode (power level below 100 kW). The dynamic behavior of the torch was characterized by the fulctuations of arc voltage and current, plasma jet radiation, and acoustic pressure. Characteristic frequencies of the arc root movement inside the torch were observed. By numerical simulation (with the numerical codeMelodie, it was shown that the position of the erosion diameter) of the axial velocity along the cathode channel near the wall. The static behavior of the torch was inverstigated for different cathode designs. The variations of voltage U with arc current I, gas flow rate G nature of the gas and cathode design were represented by semiempirical relationships established between dimensionless numbers. By dimensional analysis, the behavior of this torch was compared with that of two powerful torches: the Aerospatiale and the Plasma Energy Corporation torches. 相似文献
29.
Simon Krause Jack D. Evans Volodymyr Bon Irena Senkovska Sebastian Ehrling Paul Iacomi Daniel M. Tbbens Dirk Wallacher Manfred S. Weiss Bin Zheng Pascal G. Yot Guillaume Maurin Philip L. Llewellyn Franois-Xavier Coudert Stefan Kaskel 《Chemical science》2020,11(35):9468
Framework materials at the molecular level, such as metal–organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host–guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks'' mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases stiffness, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons. Computational modeling shows how these modifications of the building blocks tune the activation barriers within the energy landscape of the guest-free bistable frameworks. Only frameworks with free energy barriers in the range of 800 to 1100 kJ mol−1 per unit cell, and moderate yield stress of 0.6 to 1.2 nN for single ligand buckling, exhibit adsorption-induced contraction and negative gas adsorption. Advanced experimental in situ methodologies give detailed insights into the structural transitions and the adsorption behavior. The new framework DUT-160 shows the highest magnitude of NGA ever observed for nitrogen adsorption at 77 K. Our computational and experimental analysis of the energetics and mechanical response functions of porous frameworks is an important step towards tuning activation barriers in dynamic framework materials and provides critical design principles for molecular building blocks leading to pressure amplifying materials.We characterise the elastic properties of molecular building blocks and how they impact the mechanical properties of soft porous crystals. 相似文献
30.
M. Madesclaire P. Coudert V. P. Zaitsev Yu. V. Zaitseva 《Chemistry of Heterocyclic Compounds》2004,40(10):1310-1314
The interaction of (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol with a series of symmetrical ketones has been studied. As a result isomeric oxazolidines are formed in a ratio of 85:15. These oxazolidines were shown to decompose readily under the action of hydrazine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1518–1523, October, 2004. 相似文献