By Urs P. Schlunegger
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Extra info for Advanced Mass Spectrometry. Applications in Organic and Analytical Chemistry
Today, these questions can be studied more directly. The fate of the ion species of interest can be determined by systematic measurement. This has been already demonstrated in the case of l-phenyl-3-methyl-butanone (see Chapter 1 ) . There, the question was whether only one or both theoretically possible methyl cleavages occur after electron impact ionisation. This example showed that the origin and fate of ions could be detected in the case of molecular ions as well as of fragment ions. If the decomposition of consecutive ions is followed along the ion generations, the fragmentation pathways of the relative molecule concerned or of its fragments are directly obtained.
Energy W. = m v2 km γ J=mv=eBr Μ velocity ν ν - I J W . = —mv km 2 w 2eV = -*·*> j2meV m = eV The comparison in Table 1 clearly shows the direct relationship of the three criterion v, J and W ^ £ to each other. Moreover it is obvious that the velocity v, taken up by the ions in the accelerating field V, does not depend upon the geometry of the instrument. The construction and the function of the ion source and the built-in accelerating field are of no importance. It only has to produce ions of smallest possible distribution of kinetic energy, and momentum, respectively.
If the electric field is ldecreased trom Ε ^ · ^ " b to zero, then all product ions generated by metastable decompositions are focussed successively on the detector. Here again it is necessary to ask if such an energy spectrum can prove a fragment genesis. As the ion separation only resulted according to the kinetic energy W ] ^ it can be concluded that a signal in the energy spectrum may, in principle, represent any number of ions of different mass and velocity. Again, only one quantity of the equation with two unknown quantities (III) is determined and therefore the equation is unsolvable.