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Collision induced dissociation of protonated aromatic ions formed in a chemical ionization source has been studied using the technique of mass analyzed ion kinetic energy spectrometry. The observed fragmentations are concordant with those seen in the photodissociation spectra of the same ions with one significant exception. Loss of Ha is always a major collision induced dissociation process but is not observed in photodissociation spectra. This difference is not due to differences in the total amount of energy transferred in ionic excitation but to differences in the form in which the energy is supplied. Collision induced dissociation can lead to processes forbidden in photoexcitation, particularly those associated with electron unpairing in violation of the even-. even + even rule for fragmentations.

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