Multi-photon ionization (MPI) of the RNA base uracil has been studied in the wavelength range 220–270 nm, coinciding with excitation to the S2(ππ*) state. A fragment ion at m/z = 84 was produced by 2-photon absorption at wavelengths ≤232 nm and assigned to C3H4N2O+ following CO abstraction. This ion has not been observed in alternative dissociative ionization processes (notably electron impact) and its threshold is close to recent calculations of the minimum activation energy for a ring opening conical intersection to a σ(n-π)π* closed shell state. Moreover, the predicted ring opening transition leaves a CO group at one end of the isomer, apparently vulnerable to abstraction. An MPI mass spectrum of uracil-water clusters is presented for the first time and compared with an equivalent dry measurement. Hydration enhances certain fragment ion pathways (particularly C3H3NO+) but represses C3H4N2O+ production. This indicates that hydrogen bonding to water stabilizes uracil with respect to neutral excited-state ring opening.

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Electron impact ionization and ionic fragmentation of tetrahydrofuran molecules in the gas phase were studied in the energy range from ionization threshold up to 150 eV using the technique of mass spectrometry. The cation mass spectra, ionization and ionic fragmentation efficiencies were measured over this energy range. Well-resolved mass peaks were detected in the mass range 10-72 amu and assigned to corresponding ionic molecular fragments. The most abundant cation in the mass spectra is at 42 amu. Appearance energies of selected ionic fragments were also determined. Possible ionic fragmentation processes are discussed.

Photofragmentation of tetrahydrofuran molecules in the vacuum-ultraviolet region, producing excited atomic and molecular fragments, has been studied over the energy range 14-68 eV using photon-induced fluorescence spectroscopy. Excited hydrogen atoms H(n), n = 3-11, have been detected by observation of the H α to H ı lines of the Balmer series. The diatomic CH(A 2 ), CH(B 2 − ) and C 2 (d 3 g ) fragments, which are excited to low vibrational and high rotational levels are identified by their A 2 → X 2 r , B 2 − → X 2 r and d 3 g → a 3 u emission bands, respectively. Dissociation efficiency curves for CH(A 2 ) and H(n), n = 3-7, have been obtained in the photon energy ranges from their appearance thresholds up to 68 eV. The appearance energies for CH(A 2 ) and H(n), n = 3-7, have been determined and are compared with estimated fragmentation energy limits in order to discuss the possible fragmentation processes. In the present studies, superexcited states of tetrahydrofuran are found, which dissociate into the above excited atomic and molecular fragments.

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Keywords:Adenine Cluster Dissociative ionisation Hypoxanthine Multi-photon ionisation Electron impact ionisation a b s t r a c t Multi-photon ionisation (MPI) and electron impact ionisation (EII) mass spectrometry experiments have been carried out to probe unimolecular and intermolecular reactivities in hydrated adenine clusters. The effects of clustering with water on fragment ion production from adenine have been studied for the first time. While the observation of NH 4 + fragments indicated the dissociation of protonated adenine, the dominant hydration effects were enhanced C 4 H 4 N 4 + production and the suppression of dissociative ionisation pathways with high activation energies. These observations can be attributed to energy removal from the excited adenine radical cation via cluster dissociation. Comparisons of MPI and EII measurements provided the first experimental evidence supporting hypoxanthine formation in adenine-water clusters via theoretically predicted barrierless deamination reactions in closed shell complexes.