Abstract
A theory has been developed for the determination of the isomeric composition of an ionic mixture. The probability theory describing the collisionally activated decomposition (CAD) which was developed previously provided a general foundation for the present theory. Quantification was based on the cross‐sections for the collisional production of daughter ions as observed in the mass‐analysed ion kinetic energy Spectrometry (MIKES). Experimental details for the implementation of the theory have also been developed. The method has been applied to the case of C2H4O generated from butane‐l,3‐diol, which is known to be a mixture of more than one isomeric structure. The results seem to be far superior to those based on previous methods, as evidenced by the excellent internal consistency.

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