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By Ramsay W., Donnan F.G.

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1. PACHUTA AND COOKS Molecular SIMS 33 Ag Ag (2Ag*M-H-HNC0) + Scheme 2. SIMS fragmentation of nicotinamide on s i l v e r . Reproduced with permission from Ref. Ί 8 . V. CpNi(PPh )CI 3 silver support Ni(PPh ) 3 Β AgiPPh^ CpNi(PPh )CI alumina-silver support 3 Ag(PPh ) 3 l " " " " M 1 " " I I " " " " ' ! 1 m/z 300 310 320 330 340 350 360 370 380 little or no support interaction I I I I I " ' 1 " 1 " ! " " I Ί m/z 300 310 320 330 340 350 360 370 380 Ni-alumina interaction Figure 12. (A) SIMS spectrum of a nickel complex showing c h a r a c t e r i s t i c ions (Cp = C5H5).

I t i s d i f f i c u l t t o make q u a n t i t a t i v e d e t e r m i n a t i o n s o f t h e fragment y i e l d s because the f o r c e s that govern a l l the rearrangement channels a r e not known. However, t h e r e i s one i n t e r e s t i n g f e a t u r e r e l a t e d t o f r a g m e n t a t i o n t h a t we h a v e o b s e r v e d . Most o f t h e fragments formed from d i r e c t c o l l i s i o n s w i t h i n ~ 0 . 2 ps a r e t h e p a r e n t m o l e c u l e m i n u s a n H , C H , o r fy^l* T h e s e a r i s e f r o m an e n e r g e t i c c o l l i s i o n t h a t r i p s o f f part of the molecule.

These t h r e e f a c t o r s a r e e q u a l l y v a l i d f o r t h e e j e c t i o n o f e i t h e r c a r b o n monoxide, benzene or coronene. H o w e v e r , i n t h e c a s e s o f t h e l a r g e r m o l e c u l e s , we f o u n d t h a t o f t e n 2 - 3 m e t a l atoms w o u l d s t r i k e d i f f e r e n t p a r t s o f the molecule d u r i n g the e j e c t i o n process. The t i m e f o r t h e m o l e c u l e s t o e j e c t a f t e r the p r i m a r y p a r t i c l e has h i t t h e sample i s l e s s t h a n 200 femtoseconds ( f s ; I f s - l x l 0 " ^ s ) .

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