Unexpected and delayed fragmentation dynamics of the organometallic ferrocene induced by ion-collision.

We have investigated the fragmentation dynamics of the organometallic ferrocene molecule after interaction with multiply charged ions using multicoincidence mass spectrometry and quantum chemistry calculations. We observed unexpected fragmentation dynamics of the two-body breakup channels from ferrocene dications revealing a charge screening effect from the iron atom and delayed fragmentation dynamics. These observations are rationalized through the population of a specific long-lived excited state, where one positive charge is located on each cyclopentadienyl ring.

Fragmentation of pure and hydrated clusters of 5Br-uracil by low energy carbon ions: observation of hydrated fragments.

The fragmentation of the isolated 5-bromouracil (5BrU) molecule and pure and nano-hydrated 5BrU clusters induced by low energy 12C4+ ions has been studied. A comparison indicates that the environment, on the one hand, protects the system against the complete break-up into small fragments, but, on the other hand, triggers 'new' pathways for fragmentation, for example the loss of the OH group. The most striking result is the observation of several series of hydrated fragments in the hydrated cluster case, with water molecules bound to hydrophilic sites of 5BrU. This highlights the strong interaction between 5BrU and water molecules and the blocking of specific fragmentation pathways, such as the loss of the BrC2H group for example.

Multiple electron capture from isolated protein poly-anions in collision with slow highly charged ions.

Collisions of 375 keV Xe25+ ions with trapped mass/charge selected poly-anions of the cytochrome C protein (∼12.5 kDa) were studied by coupling a linear quadrupole ion trap with low-energy ion beam facility. Tandem mass spectra were recorded for the protein precursor charge states ranging from -9 to -17. The present work reports the first study of slow highly charged ion collisions with poly-anions. A high signal to noise ratio allowed the study of the intensity of single and multiple electron removal by a projectile, as well as associated neutral losses, as a function of the target charge state. Relative single and double electron detachment cross sections were found to increase with increasing charge state of the precursor anion. The experimental findings are supported by the calculations of the total electron capture cross sections, based on the classical over-the-barrier model, restricted to a simple uniformly charged linear protein structure and a near-end electron capture.

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.

Magic and hot giant fullerenes formed inside ion irradiated weakly bound C(60) clusters.

We find that the most stable fullerene isomers, C(70)-C(94), form efficiently in close-to central collisions between keV atomic ions and weakly bound clusters of more than 15 C(60)-molecules. We observe extraordinarily high yields of C(70) and marked preferences for C(78) and C(84). Larger even-size carbon molecules, C(96)-C(180), follow a smooth log-normal (statistical) intensity distribution. Measurements of kinetic energies indicate that C(70)-C(94) mainly are formed by coalescence reactions between small carbon molecules and C(60), while C(n) with n≥96 are due to self-assembly (of small molecules) and shrinking hot giant fullerenes.

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+.

Shape deformations of surface-charged microdroplets.

We present the deformation pathway of critically charged glycol and water droplets from the onset of the Rayleigh instability and compare it to numerical results, obtained for perfectly conducting inviscid droplets. In this simple model presented here, the time evolution of the droplet shape is given by the velocity potential equation. The Laplace equation for the velocity potential is solved by expanding the potential onto harmonic functions. For the part of the pathway dominated by electrostatic pressure, the calculations reproduce the experimental data nicely, obtained for both, glycol and water microdroplets. We find that the droplet shape and in particular the tips, just before charge emission, are well fitted by a lemon shape. We stress that the tip is tangent to a cone of 39 degrees and thus significantly narrower than a Taylor cone.

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.

Electron capture induced dissociation of nucleotide anions in water nanodroplets.

We have studied the outcome of collisions between the hydrated nucleotide anion adenosine 5'-monophosphate (AMP) and sodium. Electron capture leads to hydrogen loss as well as water evaporation regardless of the initial number m of water molecules attached to the parent ion (m< or =16). The yield of dianions with microsecond lifetimes increases strongly with m, which is explained from dielectric screening of the two charges by the water nanodroplet. For comparison, collision induced dissociation results in water losses with no or very little damage of the AMP molecule itself.

Collision-induced dissociation of hydrated adenosine monophosphate nucleotide ions: protection of the ion in water nanoclusters.

Fragmentation of singly charged anions of adenosine 5'-monophosphate (AMP-) induced by collisions with neutral atoms (Ne, Na) has been studied at a collision energy of 50 keV. The experiments were performed with isolated AMP- as well as with AMP- anions nanosolvated in a cluster with a given number m of water molecules. In the first case, the dominant fragmentation channels concern the loss of adenine, PO3- and H2PO4-. In the latter, loss of water molecules becomes the dominating process, and the AMP- ion is fully protected when m is larger than approximately 13. The observed fragment distributions are well described with the model of an evaporative ensemble.

Lifetimes of C60(2-) and C70(2-) dianions in a storage ring.

C60(2-) and C70(2-) dianions have been produced by electrospray of the monoanions and subsequent electron pickup in a Na vapor cell. The dianions were stored in an electrostatic ring and their decay by electron emission was measured up to 1 s after injection. While C70(2-) ions are stable on this time scale, except for a small fraction of the ions which have been excited by gas collisions, most of the C60(2-) ions decay on a millisecond time scale, with a lifetime depending strongly on their internal temperature. The results can be modeled as decay by electron tunneling through a Coulomb barrier, mainly from thermally populated triplet states about 120 meV above a singlet ground state. At times longer than about 100 ms, the absorption of blackbody radiation plays an important role for the decay of initially cold ions. The tunneling rates obtained from the modeling, combined with WKB estimates of the barrier penetration, give a ground-state energy 200+/-30 meV above the energy of the monoanion plus a free electron and a ground-state lifetime of the order of 20 s.

Two new species of litter-dwelling Metagonia spiders (Araneae, Pholcidae) document both rapid and slow genital evolution

The observation that genitalia, rather than other characters, are useful in distinguishing species has resulted in the statement that genitalia evolve relatively rapidly. In this paper we claim that relatively rapid evolution of genitalia may often be restricted to the shapes, numbers, and sizes of individual structures. In contrast, the more basic pattern, including the presence or absence of structures and their interrelationships (the bauplan), does not seem to evolve more rapidly than other (nongenital) aspects of morphology. We document this idea by contrasting two litter-dwelling pholcid species, Metagonia petropolis sp. n. and M. paranapiacaba sp. n., with their mostly leaf-dwelling congeners. Significant differences occur with regard to nongenital aspects of morphology as well as shapes of individual genital structures, but the bauplan of their genitalia is basically the same.

Speciation without changes in genital shape A case study on Brazilian pholcid spiders (Araneae Pholcidae)

Speciation in arthropods is usually coupled with marked changes in genital morphology, which explains the usefulness of genitalia in distinguishing closely related species. The present paper describes specimens that are assigned to separate species based on extreme size differences and colour pattern differences, but the shape of the genitalia is essentially identical. We argue that such cryptic species may be more common than currently assumed, but if marked morphological (non-genital) differences are missing, traditional taxonomic methodology is biased against discovering them. The two new species from the Brazilian Atlantic Forest are tentatively assigned to the genus Psilochorus: Psilochorus itaguyrussu n. sp. and Psilochorus ybytyriguara n. sp.

Highly charged clusters of fullerenes: charge mobility and appearance sizes.

Clusters of fullerenes (C60,C70)(n) are produced in a gas aggregation source and are multiply ionized in collisions with highly charged Xe(20+,30+) ions. Their stabilities and decay processes are analyzed with high-resolution time-of-flight mass spectrometry. Fullerene clusters in charge states up to q=5 have been observed and appearance sizes are found to be as small as n(app)=5, 10, 21, and 33 for q=2, 3, 4, and 5, respectively. The analysis of the multicoincident fragmentation spectra indicates a high charge mobility. This is in contrast to charge localization effects which have been reported for Ar(q+)(n) rare gas clusters. Clusters of fullerenes are found to be conducting when multiply charged.