Radiation Induced Processes in Biomolecules and Clusters in Controlled Beams

The fundamental nanoscale processes that initiate radiation damage in biological material have not yet been fully elucidated. This represents a significant barrier to developing multidimensional simulations of radiation effects that can lead to advances in radiotherapy and radioprotection. This thesis explores UV- and electron-induced processes in DNA and RNA bases. Pure and hydrated clusters are studied in order to better understand the effects of the chemical environment on the radiation response of these important biomolecules. Although extensive research has been carried out on the relaxation pathways of UV-excited nucleobases, no previous experiments have investigated bond breaking in neutral electronic excited states. This thesis reveals a new fragment ion from uracil (C3H4N2O+) that can be accessed by multi-photon ionization (MPI) but not by electron impact ionization (ElI). This provides the first experimental demonstration that neutral excited state dynamics in a nucleobase can lead to bond breaking in the aromatic ring, as predicted in recent theoretical studies. The specific excited state dynamics have not yet been identified definitively and are the subject of on-going ultrafast pump-probe experiments in collaboration with Townsend and co-workers (Heriot-Watt University). The time-resolved measurements provide new evidence supporting a theoretically predicted relaxation pathway into long-lived triplet states. Dissociative ionization of hydrated nucleobases and uracil-adenine clusters has been studied experimentally for the first time. Evidence for deamination reactions is observed in hydrated adenine complexes. The production of C3H4N2O+ fragments from uracil is strongly suppressed by clustering with water whereas the channel remains open in uracil-adenine complexes. To unravel the specific cluster-mediated dynamics and reactions responsible for these effects, further experiments are required with greater control over the cluster targets. Indeed the range of monomers and cluster configurations in neutral beams currently limits interpretations and direct comparisons with calculations. In response to this challenge, a new experiment has been built that enables radiation effects to be studied on molecules and clusters in Stark-deflected beams (MPI, ElI, and future electron attachment measurements). Early results on nitromethane beams include a demonstration that studying ElI as a function of the Stark deflector voltage can be used to deduce whether certain product ions came from monomers or from clusters