Fundamentals of tandem mass spectrometry: a dynamics study of simple C−C bond cleavage in collision-activated dissociation of polyatomic ions at low energy

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Abstract

The loss of methyl radical in collision-activated dissociation (CAD) of acetone and propane molecular ions has been studied at low energy using a tandem hybrid mass spectrometer. Although the two processes are very similar chemically and energetically, very different dynamical features are observed. Acetyl ions from acetone ion are predominantly backward-scattered, with intensity maxima lying inside and outside the elastic scattering circle, confirming our previous observation that electronically excited states are important in low-energy acetone CAD. Ethyl ions from propane ion show a forward-scattered peak maximum at a nonzero scattering angle, which is consistent with generally accepted models for vibrational excitation and redistribution of energy before dissociation. Both processes demonstrate that CAD at low energy proceeds via small-impact-parameter collisions with momentum transfer. Comparison of the present results with higher energy CAD dynamics studies and earlier work leads to some tentative general conclusions about energy transfer in these processes.