Determination of Energy-Transfer Distributions in Ionizing Ion-Molecule Collisions.

The ionization and fragmentation of the nucleoside thymidine in the gas phase has been investigated by combining ion collision with state-selected photoionization experiments and quantum chemistry calculations. The comparison between the mass spectra measured in both types of experiments allows us to accurately determine the distribution of the energy deposited in the ionized molecule as a result of the collision. The relation of two experimental techniques and theory shows a strong correlation between the excited states of the ionized molecule with the computed dissociation pathways, as well as with charge localization or delocalization.

Formation of H2 from internally heated polycyclic aromatic hydrocarbons: excitation energy dependence.

We have investigated the effectiveness of molecular hydrogen (H2) formation from Polycyclic Aromatic Hydrocarbons (PAHs) which are internally heated by collisions with keV ions. The present and earlier experimental results are analyzed in view of molecular structure calculations and a simple collision model. We estimate that H2 formation becomes important for internal PAH temperatures exceeding about 2200 K, regardless of the PAH size and the excitation agent. This suggests that keV ions may effectively induce such reactions, while they are unlikely due to, e.g., absorption of single photons with energies below the Lyman limit. The present analysis also suggests that H2 emission is correlated with multi-fragmentation processes, which means that the [PAH-2H](+) peak intensities in the mass spectra may not be used for estimating H2-formation rates.

Fragmentation of anthracene C14H10, acridine C13H9N and phenazine C12H8N2 ions in collisions with atoms.

We report experimental total, absolute, fragmentation cross sections for anthracene C14H10, acridine C13H9N, and phenazine C12H8N2 ions colliding with He at center-of-mass energies close to 100 eV. In addition, we report results for the same ions colliding with Ne, Ar, and Xe at higher energies. The total fragmentation cross sections for these three ions are the same within error bars for a given target. The measured fragment mass distributions reveal significant contributions from both delayed (≫10(-12) s) statistical fragmentation processes as well as non-statistical, prompt (∼10(-15) s), single atom knockout processes. The latter dominate and are often followed by secondary statistical fragmentation. Classical Molecular Dynamics (MD) simulations yield separate cross sections for prompt and delayed fragmentation which are consistent with the experimental results. The intensity of the single C/N-loss peak, the signature of non-statistical fragmentation, decreases with the number of N atoms in the parent ion. The fragment intensity distributions for losses of more than one C or N atom are rather similar for C14H10 and C13H9N but differ strongly for C12H8N2 where weak C-N bonds often remain in the fragments after the first fragmentation step. This greatly increases their probability to fragment further. Distributions of internal energy remaining in the fragments after knockout are obtained from the MD simulations.

Absolute fragmentation cross sections in atom-molecule collisions: scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules.

We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH(+)) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH(+) + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C6H5). Thus nonstatistical fragmentation may be an effective initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.

Ions colliding with clusters of fullerenes--decay pathways and covalent bond formations.

We report experimental results for the ionization and fragmentation of weakly bound van der Waals clusters of n C60 molecules following collisions with Ar(2+), He(2+), and Xe(20+) at laboratory kinetic energies of 13 keV, 22.5 keV, and 300 keV, respectively. Intact singly charged C60 monomers are the dominant reaction products in all three cases and this is accounted for by means of Monte Carlo calculations of energy transfer processes and a simple Arrhenius-type [C60]n(+) → C60(+)+(n-1)C60 evaporation model. Excitation energies in the range of only ~0.7 eV per C60 molecule in a [C60]13(+) cluster are sufficient for complete evaporation and such low energies correspond to ion trajectories far outside the clusters. Still we observe singly and even doubly charged intact cluster ions which stem from even more distant collisions. For penetrating collisions the clusters become multiply charged and some of the individual molecules may be promptly fragmented in direct knock-out processes leading to efficient formations of new covalent systems. For Ar(2+) and He(2+) collisions, we observe very efficient C119(+) and C118(+) formation and molecular dynamics simulations suggest that they are covalent dumb-bell systems due to bonding between C59(+) or C58(+) and C60 during cluster fragmentation. In the Ar(2+) case, it is possible to form even smaller C120-2m(+) molecules (m = 2-7), while no molecular fusion reactions are observed for the present Xe(20+) collisions.

Formations of dumbbell C118 and C119 inside clusters of C60 molecules by collision with α particles.

We report highly selective covalent bond modifications in collisions between keV alpha particles and van der Waals clusters of C(60) fullerenes. Surprisingly, C(119)(+) and C(118)(+) are the dominant molecular fusion products. We use molecular dynamics simulations to show that C(59)(+) and C(58)(+) ions--effectively produced in prompt knockout processes with He(2+)--react rapidly with C(60) to form dumbbell C(119)(+) and C(118)(+). Ion impact on molecular clusters in general is expected to lead to efficient secondary reactions of interest for astrophysics. These reactions are different from those induced by photons.

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.

Ions colliding with cold polycyclic aromatic hydrocarbon clusters.

We report the first experimental study of ions interacting with clusters of polycyclic aromatic hydrocarbon (PAH) molecules. Collisions between 11.25 keV 3He+ or 360 keV 129Xe20+ and weakly bound clusters of one of the smallest PAH molecules, anthracene, show that C14H10 clusters have much higher tendencies to fragment in ion collisions than other weakly bound clusters. The ionization is dominated by peripheral collisions in which the clusters, very surprisingly, are more strongly heated by Xe20+ collisions than by He+ collisions. The appearance size is k=15 for [C 14H10](k)2+.

The H2O(2+) potential energy surfaces dissociating into H(+)/OH(+): theoretical analysis of the isotopic effect.

We present a detailed study of the potential energy surfaces of the water dication correlating asymptotically with O((3)P) and O((1)D). Using ab initio multireference configuration interaction method, we computed a large ensemble of data, which was used to generate a fit of each potential energy surface for bending angles theta > or = 80 degrees degrees and OH distances R(OH) > or = 1.0 a.u. The fit is used to investigate the dissociation dynamics along each potential energy surface for several initial geometries corresponding to Franck-Condon transition from neutral or singly ionized water molecule. For each case, we determine the dissociation channels and we compute the kinetic energy release and angular momentum distribution of the final arrangements. Among the eight potential energy surfaces investigated here, only the lowest triplet and the three lowest singlet can lead to the formation of bound residual fragment. The dissociation of HOD(2+) presents a strong preference for OH rather than OD bond breakage. It is characterized by the isotopic ratio, defined as the number of OD(+) over the number of OH(+) residual fragments. This ratio depends strongly on the shape of each potential energy surface and on the initial conditions.

Afterglow mode and the new micropulsed beam mode applied to an electron cyclotron resonance ion source.

An increasing number of experiments in the field of low energy ion physics (<25 keV/charge) requires pulsed beams of highly charged ions. Whereas for high-intensity beams (greater than microampere) a pulsed beam chopper, installed downstream to the analyzing dipole, is used. For low-intensity beams (<100 nA) the ion intensity delivered during the pulse may be increased by operating the electron cyclotron resonance discharge in the afterglow mode. This method gives satisfactory results (i.e., average current during the beam pulse is higher than the current in the cw mode) for high charge state ions. In this paper, we report on results of the afterglow mode for beams of (22)Ne(q+), (36)Ar(q+), and (84)Kr(q+) ions. Furthermore, a new promising "micropulsed beam" mode will be described with encouraging preliminary results for (84)Kr(27+) and (36)Ar(17+) ions.

Kinematically complete study of dissociative ionization of by ion impact.

We present a kinematically complete study of dissociative ionization of D(2) by 13.6 MeV/u S(15+) ions. The experiment allows us to unravel the competing mechanisms, namely, direct single ionization, autoionization of doubly excited states, ionization excitation, and double ionization, and to analyze the corresponding electron angular distribution from fixed-in-space molecules. The conclusions are supported by theoretical calculations in which the correlated motion of all electrons and nuclei and the interferences between them are described from first principles.

Multiple ionization in the earlier stages of water radiolysis.

We have studied the fragmentation of water vapour molecules induced by collision with a Xe44+ beam at 6.7 MeV/u. From the measurement of the fragment time of flight, we show that the amount of fragmentation due to multiple ionization is very large. In the case of single ionization, we are able to reproduce accurately the experimental cross sections by calculating for each molecular level the single-ionization cross section in the framework of the CDW-EIS theory and with a diagram of dissociation modified with respect to the diagram obtained in the case of dipolar ionization. By using qualitative arguments based on the ability of the medium to neutralize a charged species, we tentatively extend our result to liquid water. From our analysis, we show that ionizations involving three or more ejected electrons could enhance the oxygen production. For the physicochemical phase we estimate that the rate of oxygen production by multiple ionization represents approximately 18% of the OH rate produced by single ionization.

Possible role of inner-shell ionization phenomena in cell inactivation by heavy ions.

The existence of a correlation between experimental probabilities of cell inactivation by charged particles and calculated probabilities for K-vacancy production in heavy atoms (C, N, O, P) of the DNA of cell nuclei is established. Both phenomena display a similar dependence upon the linear energy transfer (LET) of incident particles. In particular for low LET values, K cross sections for various incident ions have nearly the same functional dependence on ion-LET and for higher LET-values, K cross sections display maxima which look like those of inactivation cross sections. These characteristics are well-understood features of the K-ionization phenomenon, in particular the maxima of probability occur for projectile velocities near orbital velocities of the ejected electrons. The meaning of the observed correlation is discussed in terms of deposited energy and in the light of existing experimental results on cell inactivation by X-ray absorption at K-threshold. We consider a mechanism which has already been evoked to explain these photo-absorption experiments and which assumes that a K ionization triggers a double-strand break by Coulomb explosion and energy dissipation of Auger electrons. However, it is seen that K cross sections are important for C, N and O atoms but negligible for P atoms. Thus, the lesion considered here affects other atoms than those involved in the K-photoabsorption experiments. The lesion efficiency with respect to subsequent double-strand breakage and repair processes is not yet known, however one may suspect a direct link between DNA blunt ends possibly induced by such K ionizations and cell inactivation.