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The Positive Muon as a Probe in Free Radical Chemistry: by Emil Roduner

By Emil Roduner

The paintings offered here's a results of a longer collaboration with a couple of coworkers and site visitors. fairly, i want to thank Dr. P. Burkhard and Dr. W. Strub for his or her cautious paintings played for his or her Ph. D. thesis and Dr. M. Heming for his really good rules and his commitment. Very fruitful and stimulating have been collaborations with our visitors, i. e. with G. A. Brinkman and P. W. F. Louwrier from NIKHEF-K in Amsterdam, B. C. Webster, M. J. Ramos and D. McKenna from the collage of Glasgow, M. C. R. Symons, D. Geeson and C. J. Rhodes from the collage of Leicester, S. F. J. Cox and C. A. Scott from the Rutherford Appleton Laboratory in Chilton, and R. De Renzi and M. Ricco from the collage of Parma. Many priceless discussions with associates and opponents within the box helped to handle new viewpoints and to outline new objectives. I shall no longer put out of your mind my instructor and director of the unconventional chemistry team, Prof. H. Fischer, whom I desire to thank for his curiosity and energetic aid and for the nice liberty he allowed me for the making plans and association of the venture. final yet no longer least, I thank my expensive spouse Hanny and our youngsters Christian, Martin and Andrea who suffered, with out grievance, daddy's absence for therefore many hours.

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The fact that the effect is greater in certain cases in the ortho and in others in para position is less plausible. The explanation must be sought in the interaction of all substituent orbitals with all ring orbitals. In terms of perturbation theory the interaction is particularly strong when the coefficient of the AO at the substitution site is large, and when the MOs are close in energy. The latter is demonstrated nicely with X = OF 3 • Its orbitals of 7r symmetry are very low in energy and don't match the ones on the ring.

64% shorter [63]. 0009 nm) [64]. 9%. The electron. distribution adapts to the new nuclear positions. This results in a geometry relaxation on the unchanged electronic energy hypersurface. In the calculation it is taken into account by optimization of the remaining geometry parameters. 25%. Except for the methylene group the 42 symmetry plane is nearly retained. 9% at the shorter methylene C - H bond. 1). 2%. This is again in qualitative agreement with observation. It seems that the enhanced bond length to the lighter isotope gives the key to an understanding of the mass-dependent coupling constants.

We first analize the fraction transferred from Mu. 31 ) with the precursorlifetime TMu = (k~u +kLut 1 • The polarization ina stable radical (kR ~ 0) at times long compared with TMu but short compared with the inverse frequency to be observed is obtained by integration: x < m I Uu In >< n II >< II UU I k >< kim> x [cos(wRmt) - ~llenm . 32) with ~llenm = TMu(wit - wRm). I k > and II > denote the eigenstates of Mu, and In> and 1m> those of the radical. e. sh : : :; 0, c~ ~ 1} but not necessarily for Mu.

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