Anion emission from water molecules colliding with positive ions: Identification of binary and many-body processes

It is shown that negative ions are ejected from gas-phase water molecules when bombarded with positive ions at keV energies typical of solar-wind velocities. This finding is relevant for studies of planetary and cometary atmospheres, as well as for radiolysis and radiobiology. Emission of both H- and heavier (O- and OH-) anions, with a larger yield for H-, was observed in 6.6-keV 16O+ + H2O collisions. The ex-perimental setup allowed separate identification of anions formed in collisions with many-body dynamics from those created in hard, binary collisions. Most of the ani-ons are emitted with low kinetic energy due to many-body processes. Model calcu-lations show that both nucleus-nucleus interactions and electronic excitations con-tribute to the observed large anion emission yield.Comment: 5 pages, 4 figure

Anion and cation emission from water molecules after collisions with 6.6-keV 16 O+ ions

DOI: https://doi.org/10.1103/PhysRevA.100.032713arXiv link: http://arxiv.org/abs/1910.00657International audienceAnion and cation emission following water dissociation was studied for 6.6-keV $^{16}$O$^{+}$ + H$_{2}$O collisions. Absolute cross sections for the emission of all positively and negatively charged fragments, differential in both energy and observation angle, were measured. The fragments formed in hard, binary collisions appearing in peaks were distinguishable from those created in soft collisions with many-body dynamics that result in a broad energy spectrum. A striking feature is that anions and cations are emitted with similar energy and angular distributions, with a nearly constant ratio of about 1:100 for H$^{-}$ to H$^{+}$. Model calculations were performed at different levels of complexity. Four-body scattering simulations reproduce the measured fragment distributions if adequate kinetic-energy release of the target is taken into account. Providing even further insight into the underlying processes, predictions of a thermodynamic model indicate that transfer ionization at small impact parameters is the dominant mechanism for H$^{+}$ creation. The present findings confirm our earlier observation that in molecular fragmentation induced by slow, singly charged ions, the charge states of the emitted hydrogen fragments follow a simple statistical distribution independent of the way they are formed

Fragmentation processes of ionized 5-fluorouracil in the gas phase and within clusters

We have measured mass spectra for positive ions produced from neutral 5-fluorouracil by electron impact at energies from 0 to 100 eV. Fragment ion appearance energies of this (radio-)chemotherapy agent have been determined for the first time and we have identified several new fragment ions of low abundance. The main fragmentations are similar to uracil, involving HNCO loss and subsequent HCN loss, CO loss, or FCCO loss. The features adjacent to these prominent peaks in the mass spectra are attributed to tautomerization preceding the fragmentation and/or the loss of one or two additional hydrogen atoms. A few fragmentions are distinct for 5-fluorouracil compared to uracil, most notably the production of the reactive moiety CF+. Finally, multiphoton ionization mass spectra are compared for 5-fluorouracil from a laser thermal desorption source and from a supersonic expansion source. The detection of a new fragment ion at 114 u in the supersonic expansion experiments provides the first evidence for a clustering effect on the radiation response of 5-fluorouracil. By analogy with previous experiments and calculations on protonated uracil, this is assigned to NH3 loss from protonated 5-fluorouracil

Multi-photon and electron impact ionisation studies of reactivity in adenine–water clusters

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 NH4+ fragments indicated the dissociation of protonated adenine, the dominant hydration effects were enhanced C4H4N4+ 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

Evaluation of the ONIOM method for interpretation of infrared spectra of gas-phase molecules of biological interest

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Influence of ionizing radiation on molecular recognition in the gas phase: VUV and X-ray photoabsorption of antibiotic-receptor non-covalent complexes

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Absolute cross section for electron emission from uracil upon ion collision using velocity map imaging technique

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A new experimental setup to measure absolute cross section for electron emis-sion from atoms, molecules or nanoparticles upon ion collisions

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