B. A. Huber

A new‐regime Wiley–McLaren time‐of‐flight mass spectrometer

A modified version of the classic Wiley–McLaren time‐of‐flight mass spectrometer (TOFMS) is presented here. Owing to a second‐order compensation of the initial position effect, a mass resolution m/δm higher than 2000 is obtained with large ion volumes, of the order of 0.2 cm3 for Na+55 (1265 a.m.u.). Sodium clusters Na+n with n up to 530 (≂12200 a.m.u.) are separated. The spectrometer can be used for the analysis of ionized clusters in a mass range from 1 to about 20000 a.m.u. as well as for the measurement of the kinetic energy of molecular fragments after a Coulomb explosion of a molecule. The performance of this spectrometer is demonstrated with sodium clusters and molecules.

Multiply charged cluster ion crossed-beam apparatus: Multi-ionization of clusters by ion impact

An experimental setup is described, which is used to multi-ionize neutral clusters and to study their stability and the importance of different decay processes. Clusters are ionized in collisions with slow multiply charged ions (projectile charge z ranging from 1 to 30, kinetic energies ranging from 1 to 20 keV/charge). Both ion and cluster beamlines, as well as the characteristics of the analysis and detection systems, are described. Collisions with highly charged ions such as Ar8+ or Xe30+ turn out to be efficient tools in preparing clusters in high charge states without increasing significantly their internal temperature. Measurements performed in coincidence with the number of electrons stabilized by the projectile ion after the collision allowed us to control the charge and the excitation energy of the ionized system. The efficiency of the method is demonstrated for sodium clusters and C60 molecules.

Lifetimes of C602− and C702− 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.

Photodissociation of protonated amino acids and peptides in an ion storage ring. Determination of Arrhenius parameters in the high-temperature limit

We have measured the time dependence of the fragmentation of protonated amino acids and peptides upon UV excitation in an electrostatic ion storage ring. After absorption of a 266 nm photon, protonated Trp (TrpH+) has a lifetime of 10–20 μs but also a component with a millisecond lifetime is present. The long lifetime may be due to fluorescence, which leads to ions with lower excitation energy, or to the decay of the Trp+˙ radical cation formed after prompt hydrogen loss in the laser interaction region. Only one component with a lifetime of about 10 μs was detected for TyrH+. The lifetime of photoexcited PheH+ is even shorter with an upper limit of a few microseconds. For the singly protonated tripeptides (LysTrpLysH+ and LysTyrLysH+), the decay curves are found to consist of a single component that can be reproduced with an assumption of statistical decay after equilibration of the photon energy among all vibrational modes. The rate constant is expressed in the Arrhenius form in terms of the microcanonical temperature, and the decay rate is obtained by integration over the energy distribution, which has a spread corresponding to the canonical energy distribution at room temperature. The resulting deviation from exponential decay makes it possible to determine the decay parameters from a measurement at a single photon wavelength. Activation energies of Ea = 1.24 ± 0.07 and 1.5 ± 0.4 eV were determined for LysTrpLysH+ and LysTyrLysH+, respectively, with pre-exponential factors of Ad = 1011.1±0.5 and 1012.9±2.6 s−1.

Stabilities of multiply charged dimers and clusters of fullerenes

The authors find even-odd variations as functions of r (<or=7) for multiple ionization of van der Waals dimers in slow Xe(30+)+[C60]2([C60C70])-->...+[C60]2(r+)([C60C70](r+)) electron-transfer collisions. This even-odd behavior is in sharp contrast to the smooth one for fullerene monomers and may be related to even-odd effects in dimer ionization energies in agreement with results from an electrostatic model. The kinetic energy releases for dimer dissociations [predominantly yielding intact fullerenes [C60]2(r+)-->C60(r1+)+C60(r2+) in the same (r1=r2) or nearby (r1=r2+/-1) charge states] are found to be low in comparison with the corresponding model results indicating that internal excitations of the separating (intact) fullerenes are important. Experimental appearance sizes for the heavier clusters of fullerenes [C60]n(r+) (n>3 and r=2-5) compare well with predictions from a new nearest-neighbor model assuming that r unit charges in [C60]n(r+) are localized to r C60 molecules such that the Coulomb energy of the system is minimized. The system is then taken to be stable if (i) two (singly) charged C60 are not nearest neighbors and (ii) the r C60(+) molecules have binding energies to their neutral nearest neighbors which are larger than the repulsive energies for the (r-1) C60(+)-C60(+) pairs. Essential ingredients in the nearest-neighbor model are cluster geometries and the present results on dimer stabilities.

Molecular Growth Inside of Polycyclic Aromatic Hydrocarbon Clusters Induced by Ion Collisions

The present work combines experimental and theoretical studies of the collision between keV ion projectiles and clusters of pyrene, one of the simplest polycyclic aromatic hydrocarbons (PAHs). Intracluster growth processes induced by ion collisions lead to the formation of a wide range of new molecules with masses larger than that of the pyrene molecule. The efficiency of these processes is found to strongly depend on the mass and velocity of the incoming projectile. Classical molecular dynamics simulations of the entire collision process-from the ion impact (nuclear scattering) to the formation of new molecular species-reproduce the essential features of the measured molecular growth process and also yield estimates of the related absolute cross sections. More elaborate density functional tight binding calculations yield the same growth products as the classical simulations. The present results could be relevant to understand the physical chemistry of the PAH-rich upper atmosphere of Saturns moon Titan.

Fragmentation of α - and β-alanine molecules by ions at Bragg-peak energies

The interaction of keV He(+), He(2+), and O(5+) ions with isolated alpha and beta isomers of the amino acid alanine was studied by means of high resolution coincidence time-of-flight mass spectrometry. We observed a strong isomer dependence of characteristic fragmentation channels which manifests in strongly altered branching ratios. Despite the ultrashort initial perturbation by the incoming ion, evidence for molecular rearrangement leading to the formation of H(3)(+) was found. The measured kinetic energies of ionic alanine fragments can be sufficient to induce secondary damage to DNA in a biological environment.

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.

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.

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.