Dissociative multi-photon ionization of isolated uracil and uracil-adenine complexes

• UV multi-photon ionization measurements on deuterated uracil have identified a CO loss pathway that may indicate ring opening in the electronically excited neutral molecule.
• The first dissociative ionization experiments on uracil-adenine complexes have revealed that the CO loss channel is also accessible in these clusters.

Recent multi-photon ionization (MPI) experiments on uracil revealed a fragment ion at m/z 84 that was proposed as a potential marker for ring opening in the electronically excited neutral molecule. The present MPI measurements on deuterated uracil identify the fragment as C3H4N2O+ (uracil+ less CO), a plausible dissociative ionization product from the theoretically predicted open-ring isomer. Equivalent measurements on thymine do not reveal an analogous CO loss channel, suggesting greater stability of the excited DNA base. MPI and electron impact ionization experiments have been carried out on uracil-adenine clusters in order to better understand the radiation response of uracil within RNA. Evidence for C3H4N2O+ production from multi-photon-ionized uracil-adenine clusters is tentatively attributed to a significant population of π-stacked configurations in the neutral beam.

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