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Antonello S Formaggio F Moretto A Toniolo C Maran F 《Journal of the American Chemical Society》2001,123(39):9577-9584
The electron transfer to peresters was studied by electrochemical means in N,N-dimethylformamide. The reduction was carried out by three independent methods: (i) heterogeneously, by using glassy carbon electrodes, (ii) homogeneously, by using electrogenerated radical anions as the donors, and (iii) intramolecularly, by using purposely synthesized donor-spacer-acceptor (D-Sp-A) systems. Convolution analysis of the heterogeneous data led to results in excellent agreement with the dissociative electron transfer theory. The homogeneous redox catalysis data also confirmed the reduction mechanism. The cyclic voltammetries of the D-Sp-A molecules could be simulated, leading to determination of the corresponding intramolecular dissociative rate constants. Analysis of the results showed that, regardless of the way by which the acceptor is reduced, the investigated dissociative electron transfers are strongly nonadiabatic and, particularly, that the experimental rates are several orders of magnitude smaller than the adiabatic limit. A possible mechanism responsible for the observed behavior is discussed. 相似文献
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Th. Rubehn W. F. J. Müller R. Bassini M. Begemann-Blaich Th. Blaich A. Ferrero C. Groß G. Imme I. Iori G. J. Kunde W. D. Kunze V. Lindenstruth U. Lynen T. Möhlenkamp L. G. Moretto B. Ocker J. Pochodzalla G. Raciti S. Reito H. Sann A. Schüttauf W. Seidel V. Serfling W. Trautmann A. Trzcinski G. Verde A. Wörner E. Zude B. Zwieglinski 《Zeitschrift für Physik A Hadrons and Nuclei》1995,353(2):197-204
Electromagnetic fission of238U projectiles at E/A =600 and 1000 MeV was studied with the ALADIN spectrometer at the heavy-ion synchrotron SIS. Seven different targets (Be, C, Al, Cu, In, Au and U) were used. By considering only those fission events where the two charges added up to 92, most of the nuclear interactions were excluded. The nuclear contributions to the measured fission cross sections were determined by extrapolating from beryllium to the heavier targets with the concept of factorization. The obtained cross sections for electromagnetic fission are well reproduced by extended Weizsäcker-Williams calculations which include E1 and E2 excitations. The asymmetry of the fission fragments' charge distribution gives evidence for the excitation of the double giant-dipole resonance in uranium.Communicated by V. Metag 相似文献
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