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1.
Methylcyanide, CH3CN, is an important interstellar species, and therefore the accurate knowledge of precise rest frequencies for rotational transitions as well as ground-state rotational and hyperfine constants is needed. In this work the hyperfine structure of the millimeter- and submillimeter-wave spectra of CH3CN has been further investigated. In addition, accurate THz measurements have been carried out for the first time. Consequently, the present investigation allowed us to provide the most accurate ground state rotational and hyperfine parameters known at the moment for CH3C14N. To resolve the hyperfine structure of the rotational transitions observed, the Lamb-dip technique has been exploited. Both frequency-modulated and video-type detections have been employed. 相似文献
2.
We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous. 相似文献
3.
Gabriele Bonanno 《Journal of Global Optimization》1998,12(1):101-104
In this note we introduce a suitable class of functionals, including the class of integral functionals, and prove that any (strict) local minimum of a functional of this class, defined on a decomposable space, is a (strict) global minimum. So, the recent result obtained by Giner in [1] is specified and extended. 相似文献
4.
Stephan Dahlke Gabriele Steidl Gerd Teschke 《Journal of Fourier Analysis and Applications》2004,10(5):507-539
This article is concerned with frame constructions on domains and manifolds. The
starting point is a unitary group representation which is square integrable modulo a suitable
subgroup and therefore gives rise to a generalized continuous wavelet transform. Then generalized
coorbit spaces can be defined by collecting all functions for which this wavelet transform
is contained in a weighted Lp-space. Moreover, we show that a judicious discretization of the
representation leads to an atomic decomposition and to Banach frames for these coorbit spaces. 相似文献
5.
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7.
Würthwein EU Lang G Schappele LH Mayr H 《Journal of the American Chemical Society》2002,124(15):4084-4092
A literature survey on the kinetics of hydride abstractions from CH-groups by carbocations reveals a general phenomenon: Variation of the hydride acceptor affects the rates of hydride transfer to a considerably greater extent than an equal change of the thermodynamic driving force caused by variation of the hydride donor. The origin of this relationship was investigated by quantum chemical calculations on various levels of ab initio and DFT theory for the transfer of an allylic hydrogen from 1-mono- and 1,1-disubstituted propenes (XYC=CH-CH(3)) to the 3-position of 1-mono- and 1,1-disubstituted allyl cations (XYC=CH-CH(2)(+)). The discussion is based on the results of the MP2/6-31+G(d,p)//RHF/6-31+G(d,p) calculations. Electron-releasing substituents X and Y in the hydride donors increase the exothermicity of the reaction, while electron-releasing substituents in the hydride acceptors decrease exothermicity. In line with Hammond's postulate, increasing exothermicity shifts the transition states on the reaction coordinate toward reactants, as revealed by the geometry parameters and the charge distribution in the activated complexes. Independent of the location of the transition state on the reaction coordinate, a value of 0.72 is found for Hammond-Leffler's alpha = deltaDeltaG/deltaDelta(r)G degrees when the hydride acceptor is varied, while alpha = 0.28 when the hydride donor is varied. The value of alpha thus cannot be related with the position of the transition state. Investigation of the degenerate reactions XYC=CH-CH(3) + XYC=CH-CH(2)(+) indicates that the migrating hydrogen carries a partial positive charge in the transition state and that the intrinsic barriers increase with increasing electron-releasing abilities of X and Y. Substituent variation in the donor thus influences reaction enthalpy and intrinsic barriers in the opposite sense, while substituent variation in the acceptor affects both terms in the same sense, in accord with the experimental findings. Marcus theory is employed to treat these effects quantitatively. 相似文献
8.
Spoto G Gribov E Bordiga S Lamberti C Ricchiardi G Scarano D Zecchina A 《Chemical communications (Cambridge, England)》2004,(23):2768-2769
Cu(I) ions in Cu-ZSM-5 form Cu+(H2) complexes, stable at room temperature and sub-atmospheric H2 pressure, which do not have any homogeneous analogue except for matrix-isolated [Cu(eta2-H2)Cl]. Comparison with the unstable Na+(H2) adducts formed in the parent Na-ZSM-5 zeolite allow the conclusion that the Cu(I)/H2 bond is governed by sigma-pi overlap forces. 相似文献
9.
Heinz Falk Gabriele Streßler Norbert Müller 《Monatshefte für Chemie / Chemical Monthly》1988,119(4):505-508
Using a specific force field model, relative stabilities of 2,2-bipyrrole and 2,2-furylpyrrole conformers as well as of prodigiosene tautomers, configurations, and conformations, are studied. 2,2-Bipyrrole adopts anantiperiplanar conformation in accord with other theoretical calculations and experimental findings. Its rotational barrier calculated by this method compares favourably to the one derived by other means. For the parent prodigiosene the (Z)sp,sp arrangement is found to be the most stable one. The two possible tautomers within its dipyrrin fragment do not show a significant energy difference. 相似文献
10.