Michael Capron

A Multicoincidence Study of Fragmentation Dynamics in Collision of γ‐Aminobutyric Acid with Low‐Energy Ions

Fragmentation of the γ-aminobutyric acid molecule (GABA, NH(2)(CH(2))(3)COOH) following collisions with slow O(6+) ions (v≈0.3 a.u.) was studied in the gas phase by a combined experimental and theoretical approach. In the experiments, a multicoincidence detection method was used to deduce the charge state of the GABA molecule before fragmentation. This is essential to unambiguously unravel the different fragmentation pathways. It was found that the molecular cations resulting from the collisions hardly survive the interaction and that the main dissociation channels correspond to formation of NH(2)CH(2)(+), HCNH(+), CH(2)CH(2)(+), and COOH(+) fragments. State-of-the-art quantum chemistry calculations allow different fragmentation mechanisms to be proposed from analysis of the relevant minima and transition states on the computed potential-energy surface. For example, the weak contribution at [M-18](+), where M is the mass of the parent ion, can be interpreted as resulting from H(2)O loss that follows molecular folding of the long carbon chain of the amino acid.

Polycyclic aromatic hydrocarbon-isomer fragmentation pathways: Case study for pyrene and fluoranthene molecules and clusters

We report on measurements of the ionization and fragmentation of polycyclic aromatic hydrocarbon (PAH) targets in Xe(20+) + C(16)H(10) and Xe(20+) + [C(16)H(10)](k) collisions and compare results for the two C(16)H(10) isomers: pyrene and fluoranthene. For both types of targets, i.e., for single PAH molecules isolated in vacuum or for isomerically pure clusters of one of the molecules, the resulting fragment spectra are surprisingly similar. However, we do observe weak but significant isomer effects. Although these are manifested in very different ways for the monomer and cluster targets, they both have at their roots small differences (<2.5 eV) between the total binding energies of neutral, and singly and multiply charged pyrene and fluoranthene monomers. The results will be discussed in view of the density functional theory calculations of ionization and dissociation energies for fluoranthene and pyrene. A simple classical over-the-barrier model is used to estimate cross sections for single- and multiple-electron transfer between PAHs and ions. Calculated single and multiple ionization energies, and the corresponding model PAH ionization cross sections, are given.

Ion interaction with biomolecular systems and the effect of the environment

To fully understand the mechanisms of radiation damage in living tissues, a detailed knowledge of the processes occurring at the molecular level is needed. In the gas phase, most of the investigations concerning the ionization and fragmentation of biologically relevant molecular systems are performed with isolated molecules. The importance of such studies is limited to the intrinsic properties of these molecules because of the lack of a chemical environment. To probe the effect of such an environment on the behavior of small biomolecules under irradiation, the molecules (α-amino acids, adenine) were embedded into clusters. The present results, obtained with multiply charged ions, clearly indicate the protective role of the clusters since the total fragmentation yield is reduced for all systems. The surrounding molecules allow for a redistribution of the excess energy and of the charge within the cluster. In the case of adenine clusters, a new fragmentation channel is identified. Moreover, for hydrated adenine clusters, low-energy ion induced chemical reactions are observed, namely the proton transfer from the water cluster to the adenine molecule.

Ion interactions with pure and mixed water clusters

We report on collisions of highly charged Xe20+ ions with weakly bound clusters of water molecules and water/adenine mixtures. Singly and doubly charged water clusters are observed in the size range of n=1 to 65 and n=49 to 61, respectively. In contrast to other comparable systems, the dominant monomer fragment (H3O+) is formed with very low kinetic energy, hence indicating that it is formed by evaporation processes. Larger fragments are produced with larger kinetic energies due to charge-separating processes. Furthermore, water clusters are found to be protonated, only a very small amount of the non protonated dimer (H2O)2+ is observed. Excited mixed adenine/water clusters fragment by the loss of the surrounding water molecules, thus, adenine fragments are formed without water molecules attached. In addition, the adenine monomer is found to be partly protonated.

Interaction of nucleobase clusters with multiply charged ions: Insight into base pairing

We have studied the collision of low energy multiply charged ions with mixed nucleobases clusters. Mass spectra of the products show selectivity between particular nucleic bases. We could explain this enhanced stability considering base pairing occurring in DNA or RNA.

Fragmentation dynamics of complex molecules and their clusters

Complex molecular systems such as large molecules or clusters are characterised by a large number of degrees of freedom. Energies well in excess of individual thresholds for fragmentation can be stored for long times and metastable excited states become important. We will concentrate in this paper on the study of the response of such nanoscale systems, i.e. we will study excitation and fragmentation mechanisms induced by highly charged ion radiation, reflecting dynamic energy and charge flow processes. We will illustrate these relaxation processes for different molecular systems from Polycyclic Aromatic Hydrocarbons, water or biomolecule targets and their clusters in collision with multiply charged ions. We will emphasize that slow multiply charged ions provide an efficient way to study the stability of complex systems. Indeed, such ions are known to remove several electrons at large impact parameters resulting in a fast and gentle ionization.

Interaction of multiply charged ions with isolated polycyclic aromatic hydrocarbon molecules

The interaction of multiply charged ions (He2+, O3+, and Xe20+, v ≤ 0.6 a.u.) with gas phase pericondensed polycyclic aromatic hydrocarbon (PAH) molecules (pyrene and coronene) was studied. Positively charged ionic products were analyzed with a linear time-of-flight mass spectrometer.

Influence of the environment on the fragmentation of amino acids provoked by low-energy ions

With highly charged ions at low energy, molecules can be ionised on fs timescale at large distances without appreciable energy transfer. Their interaction with small amino acids leads to the fragmentation by cleavage of the weakest bond similarly to the other radiation induced fragmentation. A protective effect of the environment is observed when the molecules are embedded in a cluster of amino acids. The molecular cluster acts as a buffer dissipating the excess energy.

Molecular isomer effects in ionization and fragmentation of PAH monomers and clusters: pyrene and fluoranthene

We have investigated collisions between Xe20+ ions and the isolated polycyclic aromatic hydrocarbon (PAH) C16H10 isomers pyrene and fluoranthene or pure clusters of either pyrene or fluoranthene. We show fragment distributions and intensities for both cases and rationalize the results by means of a classical over-the-barrier (COB) model in conjunction with quantum chemistry calculations of vertical ionization energies of pyrene and fluoranthene monomers. We find that comparatively small differences in the first and second ionization energies for these isomers have significant effects on both the monomer and cluster fragment distributions.