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61.
Piotr Kirszensztejn Wlodzimierz Zmierczak 《Reaction Kinetics and Catalysis Letters》1994,52(2):467-474
This study is concerned with the effect of various amounts of Sn species in modifying the dispersity of Al2O3–SnO2 supported platinum catalysts by application of hydrogen chemisorption in a pulse chromatographic system, as well as determination of activity in water-gas shift reaction (WGS). 相似文献
62.
63.
Binding energies of ionized donor–exciton complexes in crystals of CdSe, CdTe, and ZnSe are calculated using the most realistic effective potentials available for the electron–hole interaction. 相似文献
64.
The protonated form of 1,8-bis(dimethylamino)naphthalene (DMANH(+)) consists of a rigid, aromatic framework, substituted by two amino groups that are connected by a strong, symmetric (on the NMR time-scale) hydrogen bond bridge. The reorientational motion of the molecule in dimethylformamide-d7 solution was characterized by T(1) and NOE measurements for aromatic (13)C nuclei. Treating the reorientation of DMANH(+) as anisotropic rotational diffusion of a rigid body, the diffusion tensor was determined with good accuracy. Measurements and interpretation of (15)N T(1) and NOE indicate that the proton transfer between potential minima in the hydrogen bond bridge is faster than the molecular reorientation. 相似文献
65.
Remedios González-Luque Manuela Merchán Piotr Borowski Björn O. Roos 《Theoretical chemistry accounts》1993,86(6):467-476
Summary Multiconfigurational electron correlation methods have been analyzed in order to theoretically compute the electron affinity (EA) of ozone. The near-degeneracy correlation effects, which are so important in O3 and O
3
–
, have been described using complete active space (CAS) SCF wave functions. Remaining dynamic correlation effects are computed using second-order perturbation theory (the CASPT2 method). The best calculated adiabatic value (including zero-point energy corrections), 2.19 eV, is about 0.09 eV larger than the experimental value. Comparative studies using size-consistent coupled pair functional approaches (CPF and ACPF) have also been performed. The harmonic frequencies in O
3
–
have been determined to be: 1=992, 2=572, and 3=879 cm–1, which gives a zero-point energy of 0.151 eV. 相似文献
66.
Both C(2)-P bond breaking and formation in the S-C-P(+) system do not occur according to the antiperiplanar lone pair hypothesis. Experiments using 2-phosphonio derivatives of 5-tert-butyl-1,3-dithiane and cis-4,6-dimethyl-1,3-dithiane are against the participation of higher-energy boat conformers as reactive intermediates. The results obtained support a possibility of conformational adjustment in the course of the reaction. Stereoelectronic control of the C(2)-P bond breaking and formation results from interplay of several factors. The role of the n(S)-sigma(C(2))(-)(P) and sigma(C(4,6))(-)(S)-sigma(C(2))(-)(P) hyperconjugation, as well as of the repulsive interactions between lone electron pairs pi(S) of endocyclic sulfur atoms and pi-electrons of the phenyl ring(s) connected with phosphorus, is discussed. 相似文献
67.
Małgorzata Olejnik Teresa Szprengier-Juszkiewicz Piotr Jedziniak Jan Żmudzki 《Accreditation and quality assurance》2007,12(12):637-641
In this paper, the case of FAPAS PT 0270 “Doramectin and Oxfendazole in Sheep Liver” is discussed. During evaluation of the
data received from participants (determination of total, oxidised oxfendazole residue and calculation of the sum of oxfendazole
and oxfendazole sulfone residues), significant differences were observed between the results obtained by use of two analytical
approaches. This phenomenon can be explained by the route of oxfendazole metabolism, which results in the presence of fenbendazole
in the sample. This was not predicted by the provider; consequently, not all the necessary tests on the material were conducted.
Due to the high uncertainty of the z-scores in this test, the results of the PT cannot be used for purposes of evaluation, and the benefits of participation in
PT 0270 are questionable. 相似文献
68.
69.
Owczarek E Kwiatkowski W Lemieszewski M Mazur A Rostkowski M Paneth P 《The Journal of organic chemistry》2003,68(21):8232-8235
Nitrogen, deuterium, halogen, and carbon kinetic isotope effects have been modeled for the Menshutkin reaction between methyl halides and substituted N,N-dimethylaniline at the HF/6-31G(d) level of theory augmented by the C-PCM continuum solvent model for several solvents. Systematic changes in geometries of the transition states and Gibbs free energies of activation have been found with phenyl ring substituents, solvent, and the leaving group. Kinetic isotope effects also change systematically; however, these changes are predicted to be small, inside the usual precision of the experimental measurements. On the contrary, no correlation has been found between the kinetic isotope effects and the Hammett constants for para substituents. Thus opposite to previous assumptions, our results indicate that kinetic isotope effects on the Menshutkin reaction cannot be used to predict the position of the transition state on the reaction coordinate. 相似文献
70.
The fragmentation patterns of the thioacyl derivatives of 2-aminothiazole and 2-aminobenzothiazole and of their ‘fixed structure’ imino and amino tautomeric forms give evidence of the predominance of the imino tautomer in the molecular ions of the trifluorothioacetyl compounds. On the other hand, the M+˙ ions of the thioacetyl and thiobenzoyl derivatives are mainly the amino tautomers. A rearrangement with elimination of RCN and formation of the 2-thiazolothione (2-benzothiazolothione) ion is characteristic for ail the compounds investigated. Additional evidence for the interpretation of the main fragmentation paths is provided by the mass spectra of the N-trideuteromethyl and N-deuterated derivatives, high-resolution mass spectrometry being used to determine the elemental composition of some selected peaks. 相似文献