Pulsed photodissociation in an ion cyclotron resonance trap: extending the time range for unimolecular dissociation studies of metal clusters

Optical response and shapes of charged sodium clusters; an analogue of the nuclear giant dipole response

Collective vibrations of de-localized electrons against the positive charged ionic background in sodium clusters (plasmon resonances) and the collective vibrations of protons against neutrons in nuclei (giant dipole resonances) have several features in common. However, fundamental differences exist due to differences in the two media; the nucleus is a quantum liquid whereas the metallic medium is more like a plasma with classical positive ions and quantized electrons. The similarities and differences are illustrated by results from optical response measurements for charged sodium clusters with 14 to 48 atoms.

Experimental dissociation energies of metal cluster dications and their interpretation in a liquid-drop model with empirical corrections

The dissociation energies of doubly charged silver cluster ions in the size range $9l~nl~25$ are measured by multiple collision induced dissociation. They are compared to the dissociation energies of singly charged clusters. To this end, the latter are used to calculate shell corrections in a macroscopic-microscopic model. Good agreement between the resulting predictions of the dissociation energies of the doubly charged systems and the experimental values is found, which indicates the strong influence of electronic effects on the stability of small silver clusters.

Time resolved photofragmentation of Au $_{n}^{+}$ and Ag $_{n}^{+}$ clusters (n = 9, 21)

Gold and silver cluster ions were produced by laser vaporization and stored in a Penning trap. After mass selection the cluster sizes of interest were illuminated by a laser pulse and electronically excited. Photoabsorption cross sections and fragmentation patterns were measured for photon energies of 2.3 eV to 5.2 eV. Unimolecular dissociation was observed time resolved on a microsecond to millisecond scale. Dissociation energies were deduced from the measured life times.

Chemisorption of hydrogen on charged vanadium clusters

Abstract The chemisorption of hydrogen on positively charged vanadium clusters, V n + ( n = 1–17), was studied by measuring reaction rates and saturation coverages. Vanadium clusters are produced by laser vaporization and are injected into a Penning trap. Rates of the reaction V n + +H 2 → V n + H 2 are measured by axial ejection of all ions out of the trap after variable storage times and subsequent time-of-flight detection. An odd-even effect of the reaction rate is observed with odd clusters being more reactive. Clusters with low reactivity are found to be highly stable, as reflected by the respective separation energies of atoms. The number of adsorbed hydrogen atoms, m , is determined …

Fragmentation of gold clusters stored in a penning trap

The collision-induced dissociation of positively charged gold clusters (2 to 23 atoms) stored in a Penning trap has been studied. After collisions with rare gases, excited clusters predominantly decay by emission of one or two atoms. The loss of two atoms occurs most likely through the emission of a dimer rather than a sequential evaporation. The minimum kinetic energies of clusters required to induce dissociation exhibit a pronounced odd-even effect. Clusters with an even number of delocalized electrons are more stable than the odd ones.

The temperature dependence of photoabsorption of V13+

Photoabsorption cross sections of trapped V 13 + clusters were measured for energies between 1.4 eV and 6.1 eV by use of a two-photon fragmentation technique. Using two laser pulses separated by a 100-ns delay period the cross sections of hot clusters (up to 1800 K) could be compared to the values at room temperature. Whereas sodium clusters are known to exhibit pronounced temperature dependence below 300 K, no continuation of these effects to higher temperatures was found for V 13 + .

The dissociation channels of silver clusters Agn+, 3 ≤ n ≤ 20

Abstract The low energy dissociation channels of silver cluster ions Agn+, 3 ≤ n ≤ 20 are determined by collision-induced dissociation (CID) in a Penning trap. While for most cluster sizes the first fragment cluster ion is produced by monomer evaporation, the fragment ion of small odd-sized clusters has two atoms less than their precursors indicating an evaporation of dimers. The results are compared to similar CID studies on gold cluster ions, photofragmentation patterns, abundance spectra for various silver-cluster production techniques and calculated binding energies.

Auf der Suche nach ?seltsamer? Materie

Photo fragmentation of metal clusters stored in a penning trap

Photo fragmentation studies of stored mass selected metal cluster ions of a large size range are reported. The experimental method and the data evaluation are described in detail. Gold cluster ions were produced by laser vaporization and stored in a Penning trap. After size selection they were electronically excited by irradiation with a pulsed laser beam. Relaxation by evaporation of neutral atoms and dimers was observed as a function of photon energy. From these data upper and lower limits for dissociation energies are determined for Aun + (n=3 to 23).

The trapping condition and a new instability of the ion motion in the ion cyclotron resonance trap

Abstract In analogy to the critical mass, m crit , a critical voltage, U crit , (and a general trapping parameter, π trap ) is defined, above which the ion motion in an ion cyclotron resonance (ICR) trap is unstable and the ions are lost from the trap. The theoretical values for the critical voltage are confirmed by experimental results. Singly charged gold cluster ions, Au n − , of several sizes, n = 50, 60, 76, 100, 110, and 145 (the latter corresponding to an ion mass of 28 560 u), were injected into an ICR trap, stored, and detected by axial ejection and single ion counting using a microchannel plate detector. During the storage period the trapping voltage, U , was varied for extended d…

Evidence for quasi-fission in40Ar+208Pb collisions near the coulomb-barrier

Fission-fragment angular distributions were measured in the reaction of40Ar with208Pb near the fusion barrier. For nearly symmetric mass-/charge splits we find angular distributions symmetric around θ=90 degrees, however, with unusually large anisotropies. These develop gradually into forward-backward asymmetric distributions as one moves away from mass-/charge symmetry. This indicates that non-compound fission (‘quasi-fission’) competes with true fusion-fission. The relative contribution of quasi-fission to the total fission cross section is somewhere between 51 and 85%. In the framework of the extra-push model this is equivalent to an extra-extra push energy for compound-nucleus formation…

Search for supermassive nuclei in nature

We report on a search for supermassive nuclei in nature with masses up to 107 amu. Such exotic nuclei might consist, for example, of stable strange matter, which comprises a mixture of up, down, and strange quarks, or of relic particles from the early Universe. The experiments are based on Rutherford backscattering of heavy ions, preferably238U, from various target samples. The measured parameters of a detected particle are its time-of-flight, scattering angle, and specific ionization. From this information the mass of the target nucleus can be inferred. Upper limits for the abundance of strange supermassive nuclei with massesA−4·102 to 107 amu relative to the number of nucleons were found …

Unusual excitation-energy division in quasi-fission reactions between50Ti,54Cr and58Fe with207,208Pb at the barrier

Angular distributions in quasi-fission reactions

Abstract Angular distributions for fission-like fragments were measured in the systems 50Ti, 56Fe + 208Pb by applying an off-line K X-ray activation technique. The distributions d2σ/dθdZ exhibit forward-backward asymmetries that are strongly Z-dependent. They result from a process (quasi-fission) which yields nearly symmetric masses in times comparable to the rotational period of the composite system. A method for obtaining the variance of the tilting angular momentum, K02, from these skewed, differential angular distributions is described. The results indicate that the tilting mode is not fully excited in quasi-fission reactions. The results are compared to the sum of the variances of all …

Observation of electronic and geometric shell structures of small silver clusters

Singly charged silver clusters Open image in new window in the size range n = 17 to n = 78 have been captured and stored in a Penning trap, size selected and subjected to an electron beam which leads to further ionization as well as dissociation. The resulting abundance spectra of doubly and triply charged clusters show several features: (1) A critical size for the production of doubly charged clusters which can be understood in terms of the decay pathways as previously investigated by collision induced dissociation, (2) an odd-even alternation in the abundance of singly and doubly charged clusters which inverses sign with change of charge state, (3) prominent signals for particular doubly …

A heavy-ion identification system for the detection of rare events

Abstract A large area detection system is described which consists of twelve low-pressure multi-wire proportional counters and is used in the search for exotic super-massive nuclei. The experiments are based on Rutherford backscattering of heavy ions, preferably 208Pb or 238U, from various target samples. The measured parameters of a detected particle are its time-of-flight, scattering angle, and specific ionization. From this information the mass of the target nucleus can be inferred. The present experimental sensitivity for the detection of exotic nuclei with at least twice the mass of the projectile is about 10−12 relative to the number of nucleons.

Search for strange matter by Rutherford backscattering

According to a number of suggestions, stable strange matter could exist in the form of supermassive nuclei (or 'strange nuggets')1,2. In contrast to ordinary nuclei, which contain only 'up' and 'down' quarks, a piece of strange matter should comprise a mixture of 'up', 'down' and 'strange' quarks in roughly equal proportions. Small amounts of strange matter could have survived from the early stages of the Universe1. Alternatively, strange matter might reach the Earth as a flux of strange nuggets produced in collisions of neutron stars3. Limits to the cosmic flux of strange nuggets with masses in the range from 10−4 to 250 g have been obtained in a search for light produced by the nuggets in…

Fission fragment angular distributions in the capture reactions 50Ti, 56Fe + 208Pb

The analysis of %-ray mult ip l ic i t ies measured I in coincidence with capture fission events in reactions of 26Mg through 54Cr, 58Fe, and 64Ni with 208pb in terms of Ko and~eff revealed1 that the resulting values of ~ /~e f f were rather independent of for a given system and, in a compound nucleus picture, were more in agreement with the 'shape of the non-rotating saddle than with the actually expected rotating saddle I f non-compound systenmhave to be considered these values of ~/J~ff__ shapes. suggested at least that the captured systems near the turning point from the inward radial motion to symmetric fragmentation had reached a remarkable compactness.

Trapped metal cluster ions

An overview is given of experiments with stored metal cluster ions in a Penning trap system. The setup allows axial injection of clusters produced in an external source and a time-of-flight mass analysis of the reaction products after axial ejection. The system's options include the selection of stored ions, the manipulation of their orbits, addition of reactant and buffer gases and axial optical access for laser spectroscopic studies. As described by various examples, investigations have been made with respect to the development of trapping techniques and the characterization of metal clusters in terms of their physical and chemical properties.

Collision induced dissociation of doubly charged stored metal cluster ions

Angular distributions in quasi-fission reactions: Evidence for incomplete relaxation of the tilting mode

Angular distributions of fission-like fragments have been measured for50Ti+208Pb and56Fe+208Pb collisions. Z-dependent asymmetries around Θincm= 90° preclude their interpretation in terms of compound nucleus fission with the transition state theory. Fits of the data with a simple ansatz for statistical angular momentum fluctuations (tilting) give evidence for an incomplete relaxation of the tilting mode in quasi fission reactions.

Fusion-fission in the reaction76Ge+170Er

Radiochemical yield measurements were performed to study mass- and charge distributions in the reaction of76Ge ions with170Er in the c.m. energy range from 222 MeV through 272 MeV. The magnitude of the resulting cross-section for fusion-fission is significantly lower than expected and is explained within the framework of Swiatecki's Extra-Push model.

Fission barriers of doubly charged silver clusters

The monomer evaporation energies and fission barriers of doubly charged silver cluster ions in the size range 9≤n≤25 are measured by collision induced dissociation. They are compared to the dissociation energies of singly charged silver clusters. A macroscopic liquid drop model combined with empirical microscopic corrections successfully describes the measured fission barriers.

Fragmentation pattern of gold clusters collided with xenon atoms

Abstract The dissociation channels of gold cluster ions Au n + (2 ≤ n ≤ 23) have been investigated via collision induced dissociation in a Penning trap. Excited odd cluster ions with n ≤ 15 decay by evaporation of dimers, all others decay by monomer evaporation. Information on the binding energies is deduced from these dissociation channels.

Radiative Cooling of a Small Metal Cluster: The Case ofV13+

Size-selected stored metal cluster ions, ${\mathrm{V}}_{13}^{+}$, have been heated by photoexcitation ( $\ensuremath{\lambda}\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}730$ to 229 nm) to well-defined excitation energies corresponding to temperatures between 1000 and 2100 K. A millisecond pump-probe photodissociation technique was applied to measure the time-resolved radiative cooling. The observed decay rates are directly related to the radiative energy loss and are explained quantitatively by the competing processes of photoemission and atom evaporation.

Probing cluster structures with sensor molecules: methanol adsorbed onto gold clusters

Abstract Structural, dynamical and electronic properties of the adducts formed by adsorbing methanol onto size-selected gold clusters are investigated using infrared multiple-photon dissociation spectroscopy of trapped Au n + CH 3 OH, n ⩽15, in conjunction with Car–Parrinello calculations. The C–O stretching vibration of the attached sensor molecule changes discontinuously as a function of cluster size, which is traced back to a change in dimensionality of the cluster structure.

Production and investigation of multiply charged metal clusters in a Penning trap

Singly charged gold cluster ions from a laser-vaporization source are transferred into a Penning trap and subjected to electron bombardment. The charged reaction products are analyzed by time-of-flight mass spectrometry after axial ejection from the trap. They include singly charged cluster fragments, multiply charged clusters of the initial size and multiply charged cluster fragments. The multiply charged clusters are selected and further investigated by collision induced dissociation. Two types of reactions can be distinguished: Dissociation into several charged fragments and evaporation of neutrals. Several features of multiply charged clusters relevant for future investigations are revi…

Competition between binary reactions and fusion in heavy-ion collisions at the Coulomb barrier

Mass and charge distributions for binary reaction channels have been measured for the reactions86Kr with76Ge,104Ru and130Te at the Coulomb barrier using chemical separations andγ-ray spectroscopy. These systems span the region where dynamical hindrance to complete fusion sets in. The binary reactions can be subdivided into two components associated withi) reflection from the outer potential barrier (quasielastic), andii) reseparation after passing the barrier (complex reactions). The sum of complex-reaction channels and evaporation residues from complete fusion can be reproduced by a barrier passing calculation. The fraction of the barrier passing flux leading to reseparation increases from…

The Mainz Cluster Trap

When cluster ions are stored by electromagnetic forces they are available in the gas phase for extended preparations and investigations. Over the last decade a Penning trap (Ion Cyclotron Resonance) apparatus has been constructed and further developed with respect to metal cluster research at the Institute of Physics at Mainz. It allows to capture and accumulate ion bunches injected from an external cluster source and to manipulate the ions’ motion, i.e. select and center the clusters of interest. The interactions that have been investigated include those with inert and chemically reactive gases, photons and electrons. Multiple mass spectrometric steps such as fragment ion selection can be …

External-ion accumulation in a Penning trap with quadrupole excitation assisted buffer gas cooling

Abstract A pulsed ion beam from an external source is injected into a Penning trap and accumulated by repeatedly lowering during ion capture to prevent the ions already captured from escaping. For the same reason the newly captured ions have to be cooled, which achieved by buffer gas collisions. To prevent radial on loss, the ions are exposed to azimuthal quadrupole excitation. By choosing the appropriate frequency (range) this method (selective quadrupole excitation assisted capture and centering (SQUEACE) allows a mass selection during the capture process and leads to a centering of those ions in the Penning trap. The multiple ion bunch capture results in a significant improvement in sign…

Chemisorption of hydrogen on a V5+ cluster

Abstract The binding between V 5 + and hydrogen is studied by collision induced dissociation of the cluster-adsorbate V 5 + H 2 . Vanadium clusters are produced by laser vaporization and injected into an electromagnetic ion trap. After mass separation of V 5 + , the pulsed addition of hydrogen yields V 5 + H 2 . The desorption of hydrogen is studied by acceleration of V 5 + H 2 with variable rf voltages and collisions with argon atoms. From the threshold voltage necessary for dissociation a binding energy of H 2 on V 5 + of 2.4 ± 0.3 eV is estimated. This value is consistent with a dissociative chemisorption of hydrogen.

Low-energy decay pathways of doubly charged silver clusters $Ag_{n}^{2+}$ (n = 9 - 24)

The low-energy dissociation channels of mass selected silver cluster ions Ag n 2+ (n = 9–24) are determined by collision induced dissociation (CID) in a Penning trap. While all clusters of the size n ≥ 17 evaporate neutral monomers, most smaller clusters undergo asymmetric fission of the form Ag n 2+ → Ag −3 + + Ag {3} + . However, Ag 15 2+ and Ag 11 2+ emit monomers which indicates shell or odd-even effects. The observed fragmentation pathways are different from previous reports of measurements with sputtered Ag n 2+ .

Collision induced dissociation of stored gold cluster ions

The stability of gold cluster ions Au + (2≦n≦23) has been investigated via collision induced dissociation in a Penning trap. Threshold energies and dissociation channels have been determined. The cluster stability exhibits a pronounced odd — even alternation: Clusters with an odd number of atoms,n, are more stable than the even-numbered ones. Enhanced stabilities are found for Au 3 + , Au 9 + , and Au 19 + in accordance with the Clemenger-Nilsson and the deformed jellium model of delocalized valence electrons. Excited odd cluster ions withn≦15 predominantly decay by evaporation of dimers; all others decay by monomer evaporation. From the dissociation channels estimates of the binding energi…

Decay pathway determination of even-size dicationic silver clusters: Ag162+ and Ag182+ revisited by pre-precursor selection and sequential decay

Abstract It is demonstrated how by selection of pre-precursor cluster ions Ag 2 n +1 2+ and collision-induced dissociation an ensemble of Ag 2 n 2+ can be produced, which is not contaminated by Ag n + clusters of the same size-to-charge state ratio, n / z . By use of this technique, Ag 16 2+ and Ag 18 2+ precursor ensembles have been prepared for further investigations. They are observed to decay by neutral monomer evaporation, Ag 2 n 2+ →Ag 2 n −1 2+ +Ag, and trimer fission, Ag 2 n 2+ →Ag 2 n −3 + +Ag 3 + , and show no sign of symmetric fission.

Au n+-induced decomposition of N2O

Reactions between small gold cluster ions, Au, and N2O were studied in a Penning trap mass spectrometer. Gold clusters were produced by laser vaporization and injected into a Penning trap. After reaction times of 50–7000ms the products were detected by time-of-flight mass spectrometry. For the major reaction channel, Au + N2OAu1,2N + NO+, rates of (0.9±0.1)×10−12 cm3 s−1 and (2.4±0.4)×10−12 cm3 s−1 were determined which are about a factor 500 below the collision rate. The corresponding activation energies for N2O decomposition were estimated to lie below 0.6 eV and 0.3 eV. Additional products with small branching ratios were detected, viz. the ions Au1O+, Au1N2O+, Au2N+, Au2NO+, Au2N2O+, Au…