Molecular fragmentation of pyrimidine derivatives following site-selective carbon core ionization

Ionization-site-dependent fragmentation of three cyclic biomolecules - uracil, 5-bromouracil and thymine - has been studied using electron-energy-resolved photoelectronphotoion-photoion coincidence spectroscopy. Previous studies concerning ionization site dependent fragmentation have mainly been carried out with linear molecules. The results reported here show that all studied molecules have dicationic fragmentation channels whose intensity depends on the initial core-ionization site, although these channels cover only a relatively small fraction of the total fragment yield. The present study shows on one hand, that it is often the surrounding bond(s) of the ionized atom that will break following the initial core ionization, and on the other hand, that some specific fragmentation channels can display strong site-dependency where there is no direct correlation between the ionization site and the bond breakage locations.