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131.
Generalized nuclearity conditions that are applicable in arbitrary superselection sectors of a quantum field theory and to theories with a maximal temperature are discussed. They are shown to imply the (distal) split property and to impose specific restrictions on the spectral properties of modular operators associated with local algebras and vectors of compact energy support. 相似文献
132.
The semiempirical PPP-SCF-SCI method has been adapted to even-electron, open-shell π-systems by performing the SCF calculation on the lowest triplet configuration and choosing a limited set of single electronic excitations from the latter for configuration interaction. The basic approximations and parameters of the standard PPP model were retained. The results were compared with experimental triplet-triplet absorption spectra of aromatic hydrocarbons and with more elaborate calculations available for selected systems. The reliability of the model was found to be comparable to its well-known performance in predicting the absorption spectra of closed-shell π-systems and of conjugated radicals. Triplet-state absorption spectra for various planar, conjugated biradicals were calculated and, where possible, compared with experimental data. 相似文献
133.
134.
The oxa-di-π-methane (ODPM) photorearrangement of 2-(carbomethoxy)spiro [5.5]undeca-1,3-diene-7-one (d) to d and the latter's thermal rearrangement to d were shown to be not only fully regio-and stereoselective but also to occur with complete enantiospecificity. An additional example, the 2-hydroxymethyl derivative (f) was also studied and the two systems were chemically correlated. 相似文献
135.
136.
Since predictions from high energy cross sections alone are not reliable, real parts above 10 GeV/c have been calculated from dispersion relations, using the most recent data and a simplified method. 相似文献
137.
138.
Hexabromocyclopentadiene (HBC) readily brominates α-keto and benzylic sites, apparently by bromonium ion transfer. 相似文献
139.
Ruedi Gygax Jakob Wirz Joseph T. Sprague Norman L. Allinger 《Helvetica chimica acta》1977,60(8):2522-2529
The isodynamical interconversion between the quasiplanar equilibrium conformers 1b and 1c of 1,5-bisdehydro[12]annulene requires a free energy of activation ΔG# = 4.5 ± 0.2 kcal/mol (120 K) which was determined by line shape analysis of its temperature-dependent NMR. spectrum. Force field calculations indicate that this barrier reflects the energy needed to disrupt the cyclic π-conjugation in going to the nonplanar transition state 1a . 相似文献
140.
Bernd Klingert Achim Roloff Bernhard Urwyler Jakob Wirz 《Helvetica chimica acta》1988,71(8):1858-1867
Laser flash photolysis and matrix-isolation techniques were applied to elucidate the photochemistry of the orange complex bis(pentafluorophenyl)titanocene ( = bis(η5-cyclopentadienyl)bis(pentafluorophenyl)titanium- (IV), Cp2TiIV{C6F5}2, Cp = η5-C5H5, 1 ) which is used as a polymerization photo-initiator. The primary photo-reaction of 1 is the formation of a highly reactive blue isomer X with unit quantum yield. In carefully dried and degassed benzene solution, the photoisomer X rearranges to starting material 1 with a first-order reaction, k = 5 · 103 s?1 at room temperature. X is highly reactive towards H2O, MeOH, acetone, MeCN, MeNO2, butane-1,4-diyl diacrylate, 2,2,6,6-tetramethylpiperidine N-oxide, CO, O2, and N2; absolute bimolecular rate constants range from 106 to 109 M ?1 · s?1. The primary photoisomerization 1→X is tentatively ascribed to a cyclopentadienyl ring slippage from η5 to a lower hapticity, a process that opens up coordinative unsaturation. 相似文献