Electron impact fragmentation of cytosine: partial ionization cross sections for positive fragments

We have measured mass spectra for positive ions produced by low-energy electron impact on cytosine using a reflectron time-of-flight mass spectrometer. The electron impact energy has been varied from 0 to 100 eV in steps of 0.5 eV. Ion yield curves of most of the fragment ions have been determined by fitting groups of adjacent peaks in the mass spectra with sequences of normalized Gaussians. The ion yield curves have been normalized by comparing the sum of the ion yields to the average of calculated total ionization cross sections. Appearance energies of the fragment ions have been determined, showing that the fragments 68 u-84 u have appearance energies between 10 and 11 eV, whereas fragments of 55 u and lower mass all have appearance energies above 12 eV. Most of the ion yields of 55 u and smaller show multiple onsets. Several groups of fragments have ion yield curves with nearly the same shape, clearly indicating the relevance of tautomerization in the fragmentation of cytosine.