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Major factors which determine the distribution of internal energy of a primary product ion A+, P(E)A+, at formation are delineated in terms of the quasi‐equilibrium theory and a variety of experimental evidence is offered to support these conclusions. These major factors include: the P(E) of the molecular ion, the rate constants as a function of energy, κ(E), for M+·→A+ + N0 and for competing reactions of M+·, and the partitioning of excess internal energy between A+ and N0. The ‘fluctuation effect’ on this partitioning makes P(E)A+ relatively insensitive to many structural and energy changes.
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McAdoo et al. (1974) studied this question.
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