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41.
Gunnar Sperber 《Foundations of Physics》1974,4(2):163-179
The nature of physical measurements performed on microscopic systems is discussed, and it is suggested that the procedures which are conventionally referred to as measurements fall into at least three different categories. The connection between observation processes and irreversible processes is stressed. The customary quantum mechanical treatment of irreversible processes is discussed, and its deficiencies from the philosophical point of view are criticized. The standpoint that quantum mechanics should not be considered as a basic philosophical system but rather as an immensely useful tool is defended. Some attempts at developing a more basic theory are discussed, and a hypothesis is put forward concerning the role of entropy within some possible future nonlocal hidden-variable theory. 相似文献
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A series of o-alkylphenyl alkyl ketones 1 were synthesized by different methods. The presence of a leaving group X adjacent to the carbonyl group is the special peculiarity of these ketones. Upon irradiation the keto carbonyl group of these compounds undergoes an n-pi* excitation followed by a 1,5-hydrogen migration from the o-alkyl substituent to the carbonyl oxygen atom. The thus formed 1,4-diradicals are subject to a very rapid elimination of acid HX, giving 1,5-diradicals. We called this process spin center shift. After intersystem crossing these diradicals cyclize to 1-indanones 20 in good yields. Depending on the solvent and on substituents, o-alkoxyalkyl ketones 22 or benzo[c]furanes 21 are obtained as byproducts. The mechanism of the cyclization was elucidated by quantum chemical calculations and kinetic measurements. 相似文献
46.
Alia Roy E Gast P van Gorkom HJ de Groot HJ Jeschke G Matysik J 《Journal of the American Chemical Society》2004,126(40):12819-12826
Photochemically induced dynamic nuclear polarization (photo-CIDNP) has been observed in photosystem I of spinach by (13)C magic angle spinning solid-state NMR under continuous illumination with white light. An almost complete set of chemical shifts of the aromatic ring carbons of a single Chl a molecule has been obtained which is assigned to the P2-cofactor of the primary electron donor P700. Since all light-induced (13)C NMR signals appear to be emissive, a predominance of the three-spin mixing mechanism over the differential decay mechanism is proposed. The origin of the strong contribution of the three-spin mixing mechanism and the differences with photosystem II are discussed. 相似文献
47.
Peak compression in CEC is a phenomenon that can generate very narrow peaks with extremely high efficiencies that defy current chromatographic theory. This review article summarises the content of publications in this area up to this date. Two main types of peak compression effects have been observed in the literature. First, an irreproducible and hard to control focusing effect of unclear origin, observed on strong cation exchangers. Second, a reproducible continuous stacking effect caused by sample composition induced system zones demonstrated on several types of stationary phases. 相似文献
48.
The interaction of C60 with single-wall carbon nanotubes (SWNTs) and graphite is studied experimentally by thermal desorption spectroscopy and theoretically by molecular-mechanics and molecular-dynamics calculations. The van der Waals parameters and force field for C60-graphene and C60-SWNT interactions are derived from the low-coverage C60 binding energy to the graphite surface. We use these to compare the efficiency of different mechanisms by which C60 can be encapsulated into SWNTs. 相似文献
49.
Jose Manuel?Hermida-RamónEmail author Gunnar?Karlstr?m Bengt?Nelander 《Theoretical chemistry accounts》2003,110(3):190-195
The relation between the so called basis set superposition error and intramolecular vibrational frequencies calculated at the Hartree Fock SCF level of approximation was investigated. A linear conformation of HF dimer was chosen as test system for the investigation. It was found that the direct basis set superposition error for the studied system is rather small. It was further found that the shifts are mainly determined by the geometry parameters of the system.
AcknowledgementsJ. M. H.-R. wishes to thank the Ministerio de Educación, Cultura y Deporte for the award of a research grant. 相似文献
50.
An example of the complementary use of GC-MS. GC-AED and GC-FT-IR is described for efficient structure elucidation of an unknown impurity in pharmaceutical analysis. None of the analytical techniques could solve the structure of the unknown impurity alone; identification was, however, straightforward by combining the available spectroscopic information. GC-MS provided information about structural fragments and molecular mass of the unknown compound. GC-AED was used for confirmation of the occurrence of the individual elements in the structure and to enable calculation of the empirical formula. GC-FT-IR gave valuable information regarding functional groups in the molecule. 相似文献