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21.
Vibrational excitation of SF6 by a 10.6 μm CO2 laser is shown to reduce lifetimes for SF6 dimers in supersonically expended flows. A possible utility of this phenomenon in controlling condensation rates to separate isotopes is discussed, and a kinetic analysis of the expected isotopic composition of SF6 in a supersonically expanded stream is presented. 相似文献
22.
A system of computer programs has been developed to predict and interpret the infrared spectra of molecules, ions, radicals and of chemically interacting species. The frequency parameters (or force constants) and the intensity parameters (or atomic polar tensors (APTs)) are calculated using the Gaussian-76 program for quantum mechanical calculations with a 4–31G basis set. The resultant wavenumbers and intensities have been used to predict the fundamental infrared spectra of water molecules interacting with different molecular species. The corresponding wavenumber shifts and intensity changes from the spectrum of the non-interacting water molecule are dependent upon both the geometrical orientation and the electron-donating properties of the interacting species. The intensity parameters can be further analyzed by using the charge-charge flux-overlap (CCFO) interpretation of the APTs. This interpretation is helpful in pinpointing the exact source of the perturbation that produces the intensity change. The significance is discussed of each of these CCFO terms in predicting the infrared intensities of molecules undergoing intermolecular interaction. 相似文献
23.
The interpretation of infrared intensities using the concepts of atomic polar tensors divided according to contributions from charge-charge flux-overlap (CCFO) terms appears in general to be quite useful. Here we shall illustrate this analysis for the F and H atoms in chemically related molecules to show how their properties vary for CF, CH, OF and OH bonds as R varies in RCF, RCH and ROH molecules. 相似文献
24.
Background
The determination of the osmolality of aqueous samples using a freezing point osmometer is a well-established, routine laboratory method. In addition to their use in clinical and pharmaceutical laboratories, freezing point osmometers are also employed in food testing laboratories. One application is the determination of the osmolality of milk. Although cow's milk is a natural product whose water content is approximately 87%, the osmolality of milk is a significant value when the milk is collected from a larger population of animals. This value is used in milk processing to control the water content, based on the German Food Control Regulations for Milk. 相似文献25.
26.
The Coriolis resonance between ν4 and ν7 in CH3CN and between ν1 and ν5, ν3 and ν6, and ν4 and ν7 in CD3CN has been analyzed, applying the technique developed by DiLauro and Mills, to obtain the signs of [] and the ratio of to for the interacting pairs in CD3CN. For (ν4, ν7) in both CH3CN and CD3CN, the sign of [] is found to be negative as it is also for (ν1, ν5) in CD3CN. For (ν3, ν6) the sign of this interaction term is found to be positive. For a given definition of normal coordinates the signs of these interaction terms give the relative signs of and ; our study also gives approximate values for the corresponding ratio [] 相似文献
27.
Göötz B Popović DB David DE Michl J Swiderek P 《The journal of physical chemistry. B》2006,110(11):5480-5485
Angular distributions of electrons scattered elastically and inelastically from cold solid molecular films of ethylene and nitrogen in various proportions, grown from the gas phase at different temperatures, have been studied by high-resolution electron energy loss spectroscopy. The probing depth of dipole and impact scattering has been investigated by covering the sample by overlayers of argon of increasing thickness. The angular distribution measured for elastically and inelastically dipole-scattered electrons was found to be peaked about the specular direction for all surface conditions studied, while a diffuse angular distribution was possible for electrons that underwent dipole-forbidden scattering. These results allow us to identify favorable conditions for monitoring the composition of a solid sample during the course of reactions occurring under exposure to low-energy electrons. 相似文献
28.
An improved phosphoramidite method is described to prepare oligonucleotides modified with the acyclic, achiral monomers 1. Examination of dimers, prepared on solid support or in solution, showed that phosphortriester dimers containing the allylic unit 1 were unstable towards bases, whereas phosphordiester dimers were stable. Phosphordiester dimers were obtained by replacing cyanoethyl phosphoramidites 2 with phosphoramidites 3, which gave phosphordiesters directly upon oxidation. The phosphordiester dimers were found to be stable towards capping and oxidation, but were somewhat labile towards acids. By reducing the contact time to acids during detritylation it was possible to prepare oligonucleotides containing 4 or 8 modified A, G or T units. The modified oligonucleotides hybridized to complementary DNA and RNA, although with reduced affinity (DeltaT(m) per modification -1 to -5 degrees C). 相似文献
29.
We show that several character correspondences for finite reductive groups $G$ are equivariant with respect to group automorphisms under the additional assumption that the linear algebraic group associated to $G$ has connected center. The correspondences we consider are the so-called Jordan decomposition of characters introduced by Lusztig and the generalized Harish-Chandra theory of unipotent characters due to Broué–Malle–Michel. In addition we consider a correspondence giving character extensions, due to the second author, in order to verify the inductive McKay condition from Isaacs–Malle–Navarro for the non-abelian finite simple groups of Lie types $^3\mathsf{D }_4,\mathsf{E }_8,\mathsf{F }_4,^2\mathsf{F }_4$ , and $\mathsf{G }_2$ . 相似文献
30.
The study presents first data on the delta(18)O performance of poikilohydrous lichen ground cover, and its potential impact on the isotopic composition of water fluxes arising from subjacent soil layers. As a model organism, the globally distributed lichen Cladina arbuscula was studied under laboratory conditions as well as in the field. During a desiccation experiment, delta(18)O of the lichen's thallus water and of its respired CO(2) became enriched by approximately 7 per thousand and followed a similar enrichment pattern to that expected from homoiohydrous, vascular plants. However, the observed degree of enrichment was lower in comparison to vascular plants due to (i) the lichen's inherent lower evaporative resistances; and (ii) a stronger effect of the more depleted surrounding water vapour. In lichens growing in their natural habitat, this specific pattern may show substantial variations depending on prevailing microclimatic conditions. Within a field study, thallus water delta(18)O of lichens principally proved to become more depleted when close to equilibration with the surroundings. It thereby strongly depended on the absorption of surrounding water vapour. Moreover, the results indicate that lichen mats substantially reduce evaporation rates arising from subjacent soil layers, and may alter the isotopic signal of vapour diffusing away from these layers into more depleted values. 相似文献