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101.
The title reaction has been used as an example to test the importance of using a hindered rotor treatment instead of a harmonic oscillator model for calculating vibrational partition functions corresponding to low-frequency internal rotation modes. First, a normal-mode analysis according to the Ayala and Schlegel's algorithm has been used to identify the internal rotation modes of methanethiol and the transition state structure. Then, after calculation of the energy barrier for each internal rotation, the corresponding hindered rotor partition functions have been calculated following the CW scheme of Chuang and Truhlar. The results show that the anharmonic treatment produces a rather modest improvement of the rate constants at room temperature or below. 相似文献
102.
103.
Hanns‐Dieter Amberger Lixin Zhang Hauke Reddmann Christos Apostolidis Olaf Walter 《无机化学与普通化学杂志》2006,632(15):2467-2470
Electronic Structures of Organometallic Compounds of f Elements. 64 Does the Zwitterionic Nature of the Triphenylphosphine Oxide Ligand Manifest itself in its Spectrochemical Properties? The triphenylphosphine oxide mono adducts of the moiety tris(η5‐cyclopentadienyl)lanthanide(III) (Ln(Cp)3; Ln = Pr ( 1 ), La ( 2 )) were synthesized and structurally characterized. The Ln–O distances of these compounds are noticeably shorter than those of the corresponding THF adducts. A crystal field (CF) analysis of the optical spectra of 1 leads to a low absolute value of the quadratic CF parameter which is comparable with those of [Pr(Cp)3(L)]? adducts with anionic bases but not with [Pr(Cp)3(MeTHF)]. Reasons for the latter finding are presented. 相似文献
104.
105.
Gerald Koitz Walter Fabian Hans-Werner Schmidt Hans Junek 《Monatshefte für Chemie / Chemical Monthly》1981,112(8-9):973-985
The synthesis of several 2-aminopyridines is described. The reaction of tetracyanoethylene with 3-imino-propane-carbonitrile gives 2-amino-3,4,5-tricyano-pyridines with alkyl and aryl-substituents, resp., in position 6. Nucleophilic substitution of 2-amino-6-chloro-3,5-dicyanopyridines and 2-amino-6-chloro-3,4,5-tricyano-pyridines with phenolates leads to a variety of pyridines. Spectroscopical data of absorption and fluorescence are presented and the influence of the cyano groups is discussed. The results are in good agreement with quantum chemical calculations (PPP).
Herrn Univ-Prof. Dr.A. Holasek zum 60. Geburtstag gewidmet. 相似文献
106.
Many of the interferences reported earlier for the determination of manganese in a graphite furnace were not found when a modern graphite furnace was used. At high levels of chloride matrix, an interference which was observed in the modern furnace was reduced when manganese was determined under constant temperature conditions. In this work, the sample was introduced on a tungsten wire after the graphite furnace had reached a constant, preset temperature. Drying and ashing were accomplished outside the atomization furnace, reducing contamination from matrix materials. 相似文献
107.
Margarita Valero Silvia M. B. Costa José R. Ascenso M. Mercedes Velázquez Licesio J. Rodríguez 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(4):663-677
The inclusion of the anti-inflammatory drug, Nabumetone, in -, - and hydroxypropyl--cyclodextrin (CDs) is studied using UV-VIS absorption and steady-state fluorescence emission. Binding constants and thermodynamic parameters of complex formation are determined by spectrofluorimetry. The inclusion phenomena of Nabumetone with the three cyclodextrins is compared with that of the well known similar anti-inflammatory drug Naproxen. In the case of Nabumetone pronounced differences are observed in the complexation process with each cyclodextrin whereas the respective Naproxen complexes are nearly identical. 1H-NMR experiments show that the inclusion process in Nabumetone can occur either through the substituents in the -2 (butanone) or -6 (methoxy) positions in the naphthalene ring. 相似文献
108.
Reguera Edilso Fernández-Bertrán José Balmaseda Jorge 《Transition Metal Chemistry》1999,24(6):648-654
Evidence in the literature on the synthesis of ferrous ferricyanide is critically discussed. Pyrolysis and pressure effects on Prussian Blue lead to ferrous ferrocyanide together with decomposition by-products, and not to ferrous ferricyanide. The latter compound could be a precursor in the formation of Turnbull's Blue or an excited state of Prussian Blue, but it is not a stable chemical species. 相似文献
109.
M. Angel Mateos Rocío Gálvez F. Javier Manuel de Villena José M. Pingarrón 《Mikrochimica acta》1995,120(1-4):339-349
An electroanalytical study of the herbicide propazine's reduction process in micellar solutions and oil-in-water emulsions is reported. The anionic surfactant sodium pentanesulphonate was chosen as the most suitable. The differential pulse polarograms of micellar solutions had two reduction peaks below pH 2.0, whereas only one peak was obtained above pH 2.O. Ethyl acetate was chosen as the organic solvent to form propazine emulsions. Unlike in micellar solutions, the DPP polarograms of propazine emulsions showed only one peak even at pH < 2.0, suggesting that propazine hydrolysis was hindered in the emulsified medium. The limiting current is diffusion-controlled and the electrode process is irreversible. Propazine can be determined by differential pulse polarography over the 1.0 × 10–1 – 1.0 × 10–1moll–1 and 1.0 × 10–15 – 4.0 × 10–1 moll–1 concentration ranges and the limit of detection was 2.8 × 10–1 moll–1. Of the potential interferents simazine, methoprotryne and terbutryn (alls-triazines), thiram (a dithiocarbamate), dinoseb (nitrophenolic), and heptachlor (chlorinated cyclo-diene herbicide), only the first two were significant (10% error for equimolar concentrations). The method was applied to the determination of propazine in spiked drinking water. At a concentration level of 2.0 × 10–1 moll–1 a recovery of 94 ± 6% was obtained, after tenfold concentration on Sep-Pak. 相似文献
110.
José G. Vargas 《Foundations of Physics》1986,16(10):1003-1020
The kinematic aspects of the rocket-borne clock experiment by Vessot and Levine are analyzed with the revised Robertson's test theory of special relativity (Found. Phys.
14, 625 (1984)). Besides the expected time-dilation, it is found that the intermediate steps of this experiment yield in principle Michelson-Morley type information (a relation between longitudinal and transverse length contractions) in the third order of the velocities involved, but no relativity-of-simultaneity related effects.The flat space-time test theory induces a family of spherically symmetric line elements that become the Schwarzschild line element in the relativistic case and also in theabinito rest frame of the theory. These line elements represent the same space-time manifold, but pertain in a one-to-one correspondence to the different flat space-time coordinate transformations of the test theory. The conserved energy is related to the family of local energies in the tangent plane. No deviations from the orthodoxy appear at the pertinent levels of approximation. Hence the unexplained residuals of the Vessot-Levine experiment are not due in obvious ways to kinematic and gravitational frequency shifts caused by deviations of the real coordinate transformations from the Lorentz transformations.This work was started while the author was at Departamento de Fisica, Facultad Experimental de Ciencias, Universidad del Zulia, Maracaibo, Venezuela. It was completed at the Department of Physics, Utah State University, Logan, Utah 83422. 相似文献