Laser Investigations of Stored Metal Cluster Ions

The combination of ion storage in a Penning trap and photoexcitation by pulsed lasers has proven to be a versatile instrument in metal cluster research. Recent experiments which make use of both components allow a detailed study of the clusters' properties. In particular, a new method to measure dissociation energies is reviewed and preliminary results on the competition between electron emission and neutral monomer evaporation from dianionic metal clusters are presented.

Temperature concepts for small, isolated systems: 1/t decay and radiative cooling

We report on progress in our investigations of cluster cooling. The analysis of measurements is based on introduction of the microcanonical temperature and a statistical description of the decay of an ensemble with a broad distribution in temperature. The resulting time dependence of the decay rate is a power law close to t �1 , replaced by nearly exponential decay after a characteristic time for quenching by radiative cooling. We focus on results obtained for fullerenes, both anions and cations and recently also neutral C60.

Decay pathways of small gold clusters

The decay pathway competition between monomer and dimer evaporation of photoexcited cluster ions Au + n, n = 2-27, has been investigated by photodissociation of size-selected gold clusters stored in a Penning trap. For n > 6 the two decay pathways are distinguished by their experimental signature in time-resolved measurements of the dissociation. For the smaller clusters, simple fragment spectra were used. As in the case of the other copper-group elements, even-numbered gold cluster ions decay exclusively by monomer evaporation, irrespective of their size. For small odd-size gold clusters, dimer evaporation is a competitive alternative, and the smaller the odd-sized clusters, the more likel…

Model-free determination of dissociation energies of polyatomic systems.

We describe and apply a new procedure that allows a direct determination of dissociation energies of polyatomic systems (clusters, fullerenes, polymers, and other molecules) without any modeling of the systems under investigation. As an example, we have determined the dissociation energies of a series of gold clusters Au(+)n. A comparison with values obtained from statistical models of unimolecular dissociation shows that these models significantly fail to describe the data. In contrast, the new method yields values which are an order of magnitude more accurate, thus allowing one to experimentally set benchmarks for any theory which attempts to describe activated processes.

Multisequential photofragmentation of size-selected gold cluster ions

Time-resolved fragmentation measurements have been performed on stored, size-selected gold cluster ions ${\mathrm{Au}}_{n}^{+}$ $(n=17--21)$ that have been excited up to 15 eV by multiphoton absorption. These excitation energies are far above the clusters' dissociation thresholds and initiate multistep sequential unimolecular dissociation by evaporation of neutral monomers. The measurements allow for the determination of a combination of kinetic-energy release and radiative cooling of the excited clusters. Also, previously determined model-independent values of the cluster dissociation energies are confirmed by the present measurements. The data are consistent with thermal values of the kin…

New approaches to stored cluster ions

Ion traps are “wall-less containers” which allow the extended storage of selected species. During the storage various interaction steps may be repeatedly applied. To this end no further hardware has to be added - in contrast to beam experiments. In this progress report two examples of recent developments are presented: the experiments have been performed with metal clusters stored in a Penning (ion cyclotron resonance) trap. A new experimental scheme has been developed which allows precision measurements of the dissociation energies of polyatomic species. It has been triggered by investigations on the delayed photodissociation of stored metal clusters. However, the technique is also readily…

Model-independent determination of dissociation energies: method and applications

A number of methods are available for the purpose of extracting dissociation energies of polyatomic particles. Many of these techniques relate the rate of disintegration at a known excitation energy to the value of the dissociation energy. However, such a determination is susceptible to systematic uncertainties, mainly due to the unknown thermal properties of the particles and the potential existence of 'dark' channels, such as radiative cooling. These problems can be avoided with a recently developed procedure, which applies energy-dependent reactions of the decay products as an uncalibrated thermometer. Thus, it allows a direct measurement of dissociation energies, without any assumption …

Increase in Nocturnal Blood Pressure and Progression to Microalbuminuria in Diabetes

Dissociation energies of silver clusters Agn+, n=14, 15, 16, 18

A recently developed method to determine dissociation energies has been applied to positively charged silver clusters of size n=14, 15, 16 and 18. The method uses a combination of sequential and single step decays. It requires an uncalibrated thermometer which here is provided by the evaporation rate constants of the product clusters. For this purpose, earlier measurements [J. Chem. Phys. 57 (1998) 2786] are reanalyzed with the new method. The resulting dissociation energies are compared with the liquid drop values and the measured decay rate constants with expected rate constants from detailed balance theory.

From Above Threshold Ionization to Statistical Electron Emission: The Laser Pulse-Duration Dependence ofC60Photoelectron Spectra

The photoelectron spectra of C60 ionized using a 790 nm laser with pulse durations varying from 25 fs to 5 ps have been determined. For 25 fs pulses, in the absence of fragmentation, the ionization mechanism is direct multiphoton ionization with clear observation of above threshold ionization. As the pulse duration is increased, this becomes dominated by a statistical ionization due to equilibration among the electronic degrees of freedom. For pulse durations on the order of a ps coupling to the vibrational degrees of freedom occurs and the well-known phenomenon of delayed (ms) ionization is observed.

The influence of internal degrees of freedom on the unimolecular decay of the molecule–cluster compound Au8+CH3OH

Time-resolved photodissociation measurements of the sequential reaction Au8+CH3OH→Au8+→Au7+ and the direct reaction Au8+→Au7+ have been performed for several excitation energies. The production rates and yields of the final state Au7+ in the sequential process are strongly influenced by the excitation energy deposited into the evaporated methanol molecule during the initial fragmentation step. Both the rate constants and yields can be fitted with a single parameter, the cluster–methanol binding energy.

Characterisation of Cooper pair boxes for quantum computing

We have measured and characterised superconducting single Cooper pair boxes (SCB) using superconducting single electron transistor (SET) fabricated on the same chip as an electrometer. The electrometer is sensitive to the potential changes of the SCB island and thus measures the number of excess Cooper pairs on the island. The boxes were of the Al/AlOx/Al Josephson junction type. The SCB and SET were characterised separately and the box storage performance for Cooper pairs was analysed by observing the changes in the SCB island potential while sweeping the gate voltage.

Fabrication of Nb-based superconducting single electron transistor

Abstract We have fabricated Nb/(Al-)AlOx/Nb junctions with a single electron transistor (SET) geometry using conventional e-beam lithographic technique. It was possible to reach a clearly defined superconducting gap of 0.75 meV as measured in the current vs. voltage (I–V) characteristic curve, which corresponds to Tc of 4.6 K . The Josephson coupling energy was comparable to the charging energy, EJ≈Ec=30– 40 μeV .

Determination of cluster binding energies on metal surfaces by statistics

Abstract Two simple formulae to determine binding energies of two-dimensional clusters on surfaces in thermal equilibrium are derived. One requires measurement of monomer and cluster populations and of the surface temperature. The cluster dissociation rate is derived and related to the atom hopping rate, allowing the theory to be extended to adatom populations that are not in chemical equilibrium. The result gives a recipe for determining dissociation energies that requires measurements of only two rates at a single temperature.

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.

Determination of dissociation energies by use of energy-dependent decay pathway branching ratios

Abstract We present a method for the determination of dissociation energies of polyatomic systems that undergo sequential fragmentation with energy-dependent decay pathway branching. It allows to experimentally determine the dissociation energy of any polyatomic system that shows such fragmentation behaviour without the need for a specific modelling of the system or of its fragmentation process, thus eliminating several systematic errors of traditional methods. The new method has been applied to the sequential fragmentation of Au+14 and Au+16. The resulting dissociation energies are highly accurate and in good agreement with model-free values based on rates of sequential decays.

Signature of cluster isomers in time-resolved photodissociation experiments

Abstract The unrecognized presence of structure isomers in mass-selected cluster ensembles may obstruct investigations of the systems’ intrinsic properties, since isomers differ not only in geometry, but also in other important properties. By the same token isomers are very interesting objects in the detailed study of atomic clusters. In the present work, different scenarios of isomeric coexistence are presented. They vary in the relative values of the interconversion barrier and the dissociation energies. For some idealized cases the possibility of a distinction of isomers by photodissociation experiments is discussed. In favorable situations isomeric structures may even be selected.

Recent gold cluster studies in a Penning trap

Abstract A progress report is given on the investigation of metal clusters with an ion cyclotron resonance (Penning) trap. The examples are taken from the recent studies on gold clusters. In particular, the monomer and dimer evaporation is monitored as a function of cluster size. For the particular case of Au 7 + this study is expanded to include the energy dependence of the branching ratio. In connection with the sequential decay of Au 8 + the information can be used for a model-free determination of the dissociation energy of Au 8 + . A second line of studies concerns the production, properties and storage behavior of polyanionic gold clusters. Such species have recently been produced by …

Characterisation of Cooper Pair Boxes for Quantum Bits

We have fabricated and measured single Cooper pair boxes (SCB) using superconducting single electron transistors (SET) as electrometers. The box storage performance for Cooper pairs was measured by observing the changes in the SCB island potential. We are also fabricating niobium structures, which are expected to have less problems with quasiparticle contamination than similar aluminium based devices because of the high critical temperature. The use of niobium may also reduce decoherence and thereby increase the time available for quantum logic operations.

Energy dependence of the decay pathways of optically excited small gold clusters

The pathway competition between neutral monomer and neutral dimer evaporation from optically excited odd-size gold cluster ions Au+ n, n=7–15, has been investigated as a function of cluster size and excitation energy. Gold cluster ions of these sizes are the only ones to show observable pathway competition while all other sizes exclusively evaporate either neutral monomers or neutral dimers. The investigation has been performed by photoexcitation of stored size-selected gold cluster ions with a single 10-ns laser pulse. Subsequent time-resolved observation of the delayed dissociation allows us to quantitatively determine the relative fragment yields of the respective decay channels as a fun…

Dimer dissociation energies of small odd-size clusters

The dimer dissociation energies of gold cluster ions Au + n , n = 9, 11, 13, 15 have been determined with an extension of a recently developed model-independent method. Monomer-dimer decay pathway branching ratios provide the energy dependent process which is needed in this method. The measured values are D 2 ( Au + 9 ) = 3.66(8)(9) eV, D 2 ( Au + 11 ) = 4.27(11)(8) eV, D 2 ( Au + 13 ) = 4.50(9)(7) eV and D 2 ( Au + 15 ) = 4.29(10)(6) eV.