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81.
Charlotte Froese Fischer 《International journal of quantum chemistry》1975,9(2):273-285
Results are reported for multiconfiguration Hartree–Fock studies of correlation in the lithium ground state, which maintain orthogonality of orbitals within a configuration. It is shown that when the 1s- and 2s-orbitals are fixed at their Hartree–Fock value, configurations for which Brillouin's theorem holds may be important, particularly for atomic properties other than energy. The Fermi contact term is considered as an example. 相似文献
82.
W. K. Fischer 《Fresenius' Journal of Analytical Chemistry》1967,227(2):116-120
Zusammenfassung Es wird auf eine bisher nicht beachtete Fehlermöglichkeit bei der analytischen Untersuchung und Weiterverwendung von membranfiltrierten Lösungen hingewiesen. Die üblichen Membranfilter enthalten zur Hydrophilisierung bestimmte Mengen anionaktiver Tenside, die sich nur in wechselndem Ausma\e vor dem Gebrauch eluieren lassen. Bei der Untersuchung von membranfiltrierten Flu\-, Grund- und Trinkwasserproben findet man dadurch zu hohe Tensidkonzentrationen und bei der Austestung und Verwendung sterilfiltrierter Wirkstofflösungen u. a. können betrÄchtliche Störungen eintreten. Von Fall zu Fall ist darum eine sorgfÄltige Versuchskontrolle hinsichtlich einer spezifischen Tensidwirkung nötig.
Summary Reference is made to a source of error so far unknown in analytical examinations of aqueous membrane-filtered solutions. Membrane filters usually contain a certain amount of anionic surface-active substances for hydrophilizing purposes. These substances are only partly eliminated before the use of the filter. Therefore, in samples of membrane-filtered river, underground and tap water concentrations are found higher than the actual detergent content. There may also be interferences with the testing of bio-active substances, for instance of antibiotics. Advice is given to control carefully the possible specific effect of surface-active substances during these experiments.相似文献
83.
Absolute rate constants are reported for the addition of the 1‐[(tert‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical .CHMeCO2(t‐Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain. 相似文献
84.
Reinhard Brandt 《Angewandte Chemie (International ed. in English)》1971,10(12):890-900
In this review paper, ternary fission is defined as the break-up of heavy nuclei into three fragments of approximately equal mass. This relatively new type of nuclear decay has been investigated intensively during the last decade. Muga has studied ternary fission induced by thermal neutrons in uranium. The results of his experiments are discussed in detail. Ternary fission can definitely be observed and studied in the interaction of heavy target elements with 39 MeV alpha particles, 20 GeV protons, and 300—400MeV argon ions. The ratio of binary-to-binary fission for uranium is approximately 10?4: 100 in the interaction of 39 MeV alpha particles, approximately 0.1:100 for 20 GeV protons, and 3:100 for 400MeV argon ions. A theoretical model for the interpretation of ternary fission, the “cascade model”, is described. The paper concludes with a discussion of the possible connection of ternary fission with the production and decay of still undiscovered super-heavy elements (Z = 114). 相似文献
85.
Axel Fischer Peter G. Jones Ion Neda Reinhard Schmutzler Igor V. Shevchenko 《无机化学与普通化学杂志》1994,620(5):908-913
Synthesis and Molecular Structure of new Ring Systems from 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1 reacts in two different ways to form new heterocycles. Partial oxidation of 1 with tetrachloroorthobenzoquinone furnishes the methylene-bridged λ3P, λ5P species 3 . Subsequent reactions with di- and triethylamine lead to the condensed ring system 6 with the P?C bonds connected to a central four-membered ring. Compound 6 displays crystallographic inversion symmetry, a short transannular P? P distance and an extremely distorted tetrahedral coordination geometry at the four-membered ring phosphorus atoms. 1 reacts with 7 to give the heterocycle 8 with a central eight-membered ring involving four phosphorus atoms. The eight – membered ring shows a ?bent”? crown conformation, the condensed five – membered rings display envelope conformation. 相似文献
86.
Wilfredo Hernndez Evgenia Spodine Andres Vega Rainer Richter Jan Griebel Reinhard Kirmse Uwe Schrder Lothar Beyer 《无机化学与普通化学杂志》2004,630(10):1381-1386
The N‐acyl thiourea complexes bis[N,N‐diethyl‐N′‐(p‐nitrobenzoyl)‐thioureato]copper(II) ( 1a,1b ) and bis(N,N‐diphenyl‐N′‐benzoylthioureato)copper(II) ( 2a,2b ) crystallize in each case in two modifications. X‐ray structural analysis shows that 1a and 1b are cis‐trans isomers. This is very unusual for N‐acyl thioureato complexes because with exception of one platinum(II) complex up to now only cis complexes have been found. In contrast X‐ray structural analysis of both forms 2a and 2b of the other complex shows no cis‐trans pair. Both modifications are cis complexes. In solution both isomers of the copper(II) complexes are observable by EPR spectroscopy. 相似文献
87.
The mass spectrometric behaviour of 1-aryl-5-(2-dialkylaminovinyI)-lH-tetrazoles was studied, especially 1-phenyl-5-(2-dimethylaminovinyl)-l H-tetrazole as a typical example of D- and 15N-labelled derivatives revealed a rearrangement via a carbodiimide-like intermediate ion. 相似文献
88.
Krivovichev SV Kahlenberg V Tananaev IG Kaindl R Mersdorf E Myasoedov BF 《Journal of the American Chemical Society》2005,127(4):1072-1073
A first amine-templated uranyl selenate based upon highly porous uranyl selenate nanotubules, (C4H12N)14[(UO2)10(SeO4)17(H2O)], has been prepared in the room-temperature reaction of uranyl nitrate, butylamine, and H2SeO4 in aqueous solution. The structure consists of nanometer-scale tubular [(UO2)10(SeO4)17(H2O)]14- units packed in a hexagonal-type fashion. The tubules have elliptical cross section with outer dimensions of 25 x 23 A = 2.5 x 2.3 nm. The internal free crystallographic diameter of the tubules is 12.6 A = 1.26 nm, which is comparable to the effective pore size in large-pore zeolites. This finding demonstrates the possibility of nanostructures for actinides in higher oxidation states and opens up a new area of research and exploration. 相似文献
89.
90.
Phase diagrams of nonionic foam films: new interpretation of disjoining pressure vs thickness curves
Recently we constructed phase diagrams for thin foam films stabilized by a nonionic surfactant. The idea was born by synopsis of various disjoining pressure (pi) versus thickness (h) curves of foam films resembling p-Vm isotherms of real gases. The new concept of interpreting the pi-h curves of foam films in terms of phase diagrams allows us to describe experimental observations much more precisely. Three logical consequences will be discussed here to illustrate the strength of this approach. First, the observation is explained that common black films (CBF) rupture or form a Newton black film (NBF) within a certain pressure range rather than at a defined pressure. Both observations can be rationalized by invoking a nucleation process of holes or of the thinner NBF, respectively, in close analogy to the vapor to liquid condensation. Second, the question whether the CBF to NBF transition is discrete or continuous is answered by analyzing under which conditions the supercritical state of a foam film can be reached. Third, the evidence of corresponding states is discussed. 相似文献