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91.
Bifurcations of reaction channels are related to valley-ridge inflection points and it is examined what happens when these do not coincide with transition states. Under such conditions there result bifurcating regions. There exist a number of different prototypes for such regions which are discussed explicitly on the basis of the pertinent Taylor expansions. When bifurcations occur close enough to transition states then there result bifurcating transition regions. An example for a bifurcating transition region is exhibited which is obtained from a quantum mechanical ab initio calculation for the ring opening of cyclopropylidene to aliene. In general there exist no orthogonal trajectory patterns which could serve as simplified models for channel bifurcations.Operated for the U.S. Department of Energy by Iowa State University under Contract No. W-7405-ENG-82. This work was supported by the Office of Basic Energy Sciences 相似文献
92.
93.
Klaus Behmel Manfred Schulze und Ulrich Annagat 《Fresenius' Journal of Analytical Chemistry》1968,241(1):1-4
Zusammenfassung Eine einfache und genaue Methode zur Bestimmung von Si-H- und Si-Si-Gruppen wird vorgeschlagen, die auf alkalischer Hydrolyse der Substanz in einem verschlossenen und evakuierten Kolben und AuswÄgen des dem entwickelten Wasserstoff entsprechenden Wasservolumens beruht. Bei H-Gehalten von 1–2% betrÄgt die Genauigkeit ± 0,03% (abs.).
Herrn Prof. Dr. E. Asmus zum 60. Geburtstag gewidmet. 相似文献
Note on the quantitative determination of Si-H- and Si-Si-groups
A simple, robust and surprisingly exact method for the quantitative determination of Si-H- or Si-Si-groups is based on alkaline hydrolysis of the Si-H- or Si-Si-containing substances in a sealed and evacuated vessel and weighing of the volume of water equivalent to the developed volume of hydrogen. The accuracy is ± 0.03% (abs.) with H contents of 1–2%.
Herrn Prof. Dr. E. Asmus zum 60. Geburtstag gewidmet. 相似文献
94.
95.
Raab V Harms K Sundermeyer J Kovacević B Maksić ZB 《The Journal of organic chemistry》2003,68(23):8790-8797
1,8-bis(dimethylethyleneguanidino)naphthalene (DMEGN), the second example of a peralkyl guanidine "proton sponge" based on the 1,8-naphthalene backbone, was prepared and fully characterized. The crystal structure analysis of monoprotonated DMEGN reveals an unsymmetrical intramolecular hydrogen bridge. A decrease in the basicity with respect to the noncyclic parent 1,8-bis(tetramethylguanidino)naphthalene was found. Nevertheless, a new proton sponge provides a new crossbar in the ladder of highly basic neutral organic compounds. A detailed theoretical study of DMEGN and related cyclic guanidines explains this surprising experimental result. Homodesmotic reactions reveal that the intramolecular hydrogen bond contributes effectively 10 kcal/mol to proton affinity of DMEGN. 相似文献
96.
Structures of Charge-Perturbed or Sterically Overcrowded Molecules. 16. Tetracyanoethylene Sodium Dimethoxyethane The Single crystal structure of [(NC)2C? C(CN)2?·Na⊕(H3CO? CH2CH2? OCH3)]∞ reveals two formula units within the triclinic (P1 ) unit cell. The tetracyanoethylene radical anions are arranged along parallel double layers, which are shifted relative to each other, and in between which are interspersed the sodium counter cations and their dimethoxyethane ligands. The distances within the double layers amount to 300 pm and the ones between them to 385 pm. The six-fold coordinated Na⊕ centers are surrounded by four radical anions with contact distances Na…?N between 250 and 254 pm as well as by a twofold solvent ligand with Na…?O of 238 and 241 pm. Due to the electron transfer to the acceptor molecule, its (NC)2C-halves twist by 8° and the bond lengths of the N?C? C subunits, bent by each 3°, are shortened up to 2 pm. The structural parameters are compared to those of the analogous potassium salt [TCNE?K⊕DME], of the dianion , of the sodium salts [(NC)3C?Na⊕]∞ as well as [(NC)2C? C(CHCH)2? C(CN)2?Na⊕]∞ and, in addition, are discussed based on geometry-optimized MNDO calculations. 相似文献
97.
Vijayasarathi Nagarajan Barbara Müller Oksana Storcheva Klaus Köhler Andreas Pöppl 《Research on Chemical Intermediates》2007,33(8):705-724
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin
echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data
of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental
and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands. 相似文献
98.
Klaus Beyermann 《Fresenius' Journal of Analytical Chemistry》1961,183(2):91-107
Zusammenfassung Es wird gezeigt, daß mit Hilfe von Fuchsin eine colorimetrische Bestimmung von Rhenium in Mengen von 1–10 g mit einer Standardabweichung von 0,1 g möglich ist. Ein Abtrennungsverfahren, bestehend aus Sublimation des Rheniums und dessen Extraktion mit Tetraphenylarsoniumchlorid gestattet die Anwendung der colorimetrischen Methode zur Erfassung von Rheniumgehalten von 10–1 bis 10–4% in Mineralien und technischen Produkten.Herrn Prof. Geilmann und Herrn Prof. Bock danke ich für anregende Diskussionen. Herrn Prof. Strassmann und Herrn Dr. Herrmann bin ich für die Erlaubnis zur Benutzung der Hilfsmittel der radiochemischen Abteilung und für gegebene Ratschläge zu Dank verpflichtet. 相似文献
99.
Humic substances were analysed by atmospheric pressure chemical ionisation (APCI) and electrospray ionisation (ESI) mass spectrometry in positive and negative modes. Using APCI the average m/z range of humic substances was reduced 5-fold compared to ESI. High-resolution time-of-flight mass spectrometry revealed the formation of multiply charged molecules in the ESI mode. Moreover, it was possible to obtain daughter ion mass spectra of humic substances by nanospray tandem mass spectrometry. The size-exclusion chromatography elution profile of humic substances was highly influenced by the pH of the analyte solution. By contrast, the pH had no significant influence on the observed mass spectra of humic substances. 相似文献
100.
Klaus Hoechsmann 《Rendiconti del Circolo Matematico di Palermo》1995,44(1):5-20
Let ζ be a primitivesp-th root of unity for a primep>2, and consider the group Ω(ζ) of cyclotomic units in the ringR(ζ)=ℒ[ζ+ζ-1]. This paper deals with the image of Ω(ζ) in the unit group ofR(ζ)/qR(ζ), whereq is a prime ≠p. In particular, it obtains criteria for this image to be essentially everything, and a lower bound on the density of primesp (withq fixed) for which it cannot be. These results have a direct bearing on previous work about units in integral group rings for
cyclic groups of orderpq.
Work supported in part by an operating grant from NSERC (Canada). 相似文献