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91.
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Fabian WM 《The Journal of organic chemistry》2002,67(21):7475-7482
The site of nucleophilic addition to five-membered heterocyclic 2,3-diones (4-iminomethylfuran-2,3-dione A1 and 4-formyl-pyrrole-2,3-dione B1) is studied by density functional theory calculations (B3LYP/6-31G) with water as the nucleophile. Both uncatalyzed and water-assisted 1,2-addition to the lactone (lactam) and the keto carbonyl group, and conjugate addition to C5 of the heterocycle and the heteroatom of the 4-iminomethyl (formyl) moiety are considered. In addition, concerted and stepwise ring fission of the lactone (lactam) ring is also treated. The effect of solvation (aqueous solution) is taken into account by the polarizable continuum model (PCM) and the Poisson-Boltzmann SCRF method (PB-SCRF), as well as explicit water molecules. Only this latter approach yields meaningful activation free energies. Barriers for addition of H2O increase in the order 1,4-addition to C5 < addition to the lactone (lactam) carbonyl < hydration of the 3-keto group. No reaction path for concerted water-assisted ring opening could be found. 相似文献
95.
We consider a one-dimensional charge density wave insulator formed by umklapp processes in a quarter-filled band. The spectrum of the model consists of gapless, uncharged excitations carrying spin +/- 1/2 (spinons) and gapped, spinless excitations carrying charge -/+ signe/2 (solitons and antisolitons). We calculate the low-energy behavior of the single-electron Green's function at zero temperature. The spectral function exhibits a featureless scattering continuum of two solitons and many spinons. The theory predicts that the gap observed by angle resolved photoemission is twice the activation gap in the dc conductivity. We comment on possible applications to PrBa(2)Cu(3)O(7) and to the Bechgaard salts. 相似文献
96.
Nontrivial steady flows have recently been found that capture the main structures of the turbulent buffer layer. We study the effects of polymer addition on these "exact coherent states" (ECS) in plane Couette flow. Despite the simplicity of the ECS flows, these effects closely mirror those observed experimentally: Structures shift to larger length scales, wall-normal fluctuations are suppressed while streamwise ones are enhanced, and drag is reduced. The mechanism underlying these effects is elucidated. These results suggest that the ECS are closely related to buffer layer turbulence. 相似文献
97.
R.-D. Herzberg N. Amzal J.E. Bastin F. Becker P.M.T. Brew P.A. Butler A.J.C. Chewter J.F.C. Cocks O. Dorvaux K. Eskola J. Gerl P.T. Greenlees N.J. Hammond K. Hauschild K. Helariutta F. Heßberger M. Houry A. Hürstel R.D. Humphreys G.D. Jones P.M. Jones R. Julin S. Juutinen H. Kankaanpää H. Kettunen T.L. Khoo W. Korten P. Kuusiniemi Y. Le Coz M. Leino A.P. Leppänen C.J. Lister R. Lucas M. Muikku P. Nieminen R.D. Page T. Page P. Rahkila P. Reiter Ch. Schlegel C. Scholey G. Sletten O. Stezowski Ch. Theisen W.H. Trzaska J. Uusitalo H.J. Wollersheim 《The European Physical Journal A - Hadrons and Nuclei》2002,15(1-2):205-208
In-beam conversion electron spectroscopy experiments have been performed on the transfermium nuclei 253, 254No using the conversion electron spectrometer SACRED in nearly collinear geometry in conjunction with the gas-filled separator
RITU at the University of Jyv?skyl?. The experimental setup is discussed and the spectra are compared to Monte Carlo simulations.
The implications for the ground-state configuration of 253No are discussed.
Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002
RID="a"
ID="a"e-mail: rdh@ns.ph.liv.ac.uk
RID="b"
ID="b"Present address: GANIL, F-14021 Caen, France.
RID="c"
ID="c"Permanent address: IReS Strasbourg, IN2P3-CNRS, F-67037-Strasbourg, France.
RID="d"
ID="d"Present address: CEA/DIF DCRE/SDE/LDN F-91680 Bruyeres-le-Chatel.
RID="e"
ID="e"Present address: Daresbury Laboratory, Daresbury WA4 4AD, UK.
RID="f"
ID="f"Permanent address: IPN Lyon, IN2P3-CNRS, F-69037 Lyon, France. 相似文献
98.
99.
P. Aguer G. Bastin A. Charmant Y. El Masri P. Hubert R. Janssens C. Michel J.P. Thibaud J. Vervier 《Physics letters. [Part B]》1979,82(1):55-59
Lifetimes for high-spin levels (between about 10 and 30 ?) in 154Er have been measured by the recoil-distance method. Non-collective, moderately collective and collective E2 transitions from states with lifetimes between at most 10 and 400 ps have been found. All available data on this nucleus are discussed within the framework of the oblate coupling scheme with the addition of collective degrees of freedom. 相似文献
100.
Frennet A Visart de Bocarmé T Bastin JM Kruse N 《The journal of physical chemistry. B》2005,109(6):2350-2359
The aim of this paper is to demonstrate the importance of providing time-resolved information in catalysis research. Two truly in situ methods will be presented and compared for their merits and drawbacks: chemical transient kinetics (CTK) and pulsed field desorption mass spectrometry (PFDMS). The presentation will be given by way of example choosing the syngas (CO/H2) reaction over cobalt-based catalysts as a catalytic process. Despite numerous efforts in the past, the mechanism of this reaction is still under debate. In CTK the reaction is studied on a metal-supported catalyst under flow conditions in a pressure range extending from atmospheric pressure down to 100 Pa. Sudden changes in the partial pressures of the reactants then allow following the relaxation to either steady-state conditions ("transients") or cleanoff ("back transients"). In PFDMS short field pulses of several volts per nanometer are applied to a model catalyst which resembles a single metal particle grain (a "tip"). These pulses intervene during the ongoing reaction under flow conditions at pressures ranging from 10(-1) to 10(-5) Pa and cause field desorption of adsorbed species. This method is particularly suited to detect reaction intermediates in a time-dependent manner since the repetition frequency of the pulses can be systematically varied. It is shown that both methods lead to complementary results. While CTK allows conclusions on the mechanism of CO hydrogenation by following the time-dependent formation of hydrocarbon species, PFDMS provides insight into the initial steps leading to adsorbed CxHy species. A quantitative assessment of the CTK data allows the demonstration that the catalyst under working conditions is in an oxidized rather than metallic state. The initial steps to oxidation are also traced by PFDMS. Most importantly, however, CTK results allow formulation of a reaction mechanism that is common for both hydrocarbon and oxygenate formation and is based on the occurrence of a formate-type species as the most abundant surface intermediate. 相似文献