Continuous cluster beam

In the gas-aggregation source a metal is vaporized and introduced in a flow of cold inert gas in which the vapor becomes highly supersaturated. Clusters are mainly produced by successive single-atom addition in the build-up of larger species. This type of source has been used to produce continuous cluster beams of alkali elements. By using two separate ovens in the source, each containing separate materials, clusters with two elements can be produced as Ceo covered with alkali metals [83]. The limitation of this type of source is that only metals with a low melting point can be studied. 

The setup at the Universitat Rostock utilizes an ACIS to produce a continuous cluster beam (see Fig. 3.9). The metal vapor plasma is created in the cylindrical cathode of target material. The fabricated clusters, neutral and charged are expanded through an exit nozzle and collimated by an aerodynamic lens attached to the source. The clusters then flow through a secondary pumping stage bracketed by two skimmers and are size selected by an electrostatic quadrupole deflector for deposition. 

Barber et al. introduced FAB in 1981. In this technique, bombardment of a liquid target surface by a beam of fast atoms such as xenon or argon, causes the continuous desorption of ions that are characteristic of the liquid. In a typical FAB spectrum, the analyte ion is usually formed as protonated or cationized ions in positive FAB, and deprotonated ions in negative FAB mode. A few fragmented ions may also be formed. The spectrum usually contains peaks from the matrix, such as protonated matrix clusters of glycerol if it is used as the matrix solvent. FAB utilizes a liquid matrix such as glycerol. The matrix is used to enhance sensitivity and ion current stability. 

The laser vaporization approach allows the use of even the most refractory target materials. The source configuration used in Fig. 1 involves a target rod that is rotated and translated in a continuous screw motion to expose fresh metal to the laser beam. This has been found necessary to provide acceptable pulse-to-pulse reproducibility. Target rods of refractory metals, semiconductors, carbon, polyethylene, alumina, and alloys have all been vaporized successfully to make clusters in many laboratories. For some materials a disk target is preferred due to the ease in sample preparation. Molecular solids, liquids, and solutions could also be used, though care must be taken to consider the additional complex plasma chemistry one is likely to encounter. 

A systematic view of the relevant elements is depicted in Figure 17.10. The deposited clusters can be exposed to different reactant gases by two kinds of valves. First, they can be exposed isotropically to e.g. O2 by a commercial, ultra-high vacuum (UHV) compatible, variable leak valve. Second, reactant molecules (e.g. CO) can be introduced via a pulsed molecular beam produced by a piezo-electric driven, pulsed valve. This pulsed valve has a high pulse-to-pulse stability (time profile), and allows the study of catalytic processes on supported clusters at relatively high pressures (up to 10 mbar). Furthermore, a stainless steel tube is attached to the pulsed nozzle in order to collimate the molecular beam and to expose the reactant molecules to the substrate only. The pulse duration at the position of the sample can, in principle, be varied from 1 ms up to continuous operation. For the experiments described below a constant pulse duration of about 100 ms was used. The repetition rate of the pulsed valve can be up to 100 Hz. The experiments were carried out at 0.1 Hz the 10 s interlude allows the reactant gas to be pumped completely. 

Fig. 1.52. Typical experimental setup for a pulsed molecular beam experiment for studying the catalytic properties of size-selected clusters on surfaces. It mainly consists of a pulsed valve for the generation of a pulsed molecular beam and a differentially pumped, absolutely calibrated quadrupole mass spectrometer. The length of the valve extension tube is adjusted to obtain a beam profile of similar dimensions as the sample under investigation. A typical time profile is also shown. It can be adjusted up to continuous operation. The pulse-to-pulse stability is better than 1%...

The cathode is continuously rotated by means of an external motor in order to allow constant ablation conditions for all pulses and a homogeneous consumption of the rod. Higher deposition rates can be obtained by substituting the simple cylindrical nozzle with a more complex one (called focuser) as described in Reference 28. Exploiting inertial aerodynamic effects [28,29], the focuser reduces the angular semiaperture of the beam from 12° to less than 1° concentrating the cluster on the center of the beam. 

In many respects the development of tunable infrared and ultraviolet laser sources when combined with molecular beam expansions, mrurked the start of the modern or contemporary period of cluster studies. First, it offered the opportunity to selectively excite specific rovibrational or rovibronic levels in a complex. Second, variations in the spectra (linewidth, intensity and frequency) gave insight into dynamical behavior and the presence of nearby perturbing states. 3 Finally, the availability of widely tunable sources has enabled the experimentalist to select quantum states that would provide the maximum information content on a cluster system, an impetus that continues to drive the development of new lasers and laser systems. As this is an extremely wide field of research, primary emphasis in this chapter will be placed on vibrational spectroscopic studies of neutral and ionic clusters. 

While the use of direct absorption methods has grown, indirect action spectroscopic methods continue to be widely and successfully used in the study of neutral molecular clusters. As mentioned earlier, there are two commonly used detection methods, mass spectrometers and bolometers. Because of the variety of mass-spectroscopic methods, there is an equally wide range of techniques used in neutral cluster spectroscopy. One of the oldest among these involves electron-impact mass spectrometry of a cw neutral beam combined with vibrational predissociation spectroscopy using a tunable cw or pulsed laser. The advent of continuously tunable infrared sources (such as color center lasers and LiNbOa optical parametric oscillators) allowed for detailed studies of size and composition variation in neutral clusters. However, fragmentation of the clusters within the ionizer of the mass spectrometer, severely limited the identification of particular clusters with specific masses. Isotopic methods were able to mitigate some of the limitations, but only in a few cases. 

Indirect methods can also use mass spectrometers as detectors. As noted above fragmentation is a potentially severe problem that must be taken into consideration. Both continuous and pulsed beam techniques can be used. A particularly novel approach has been developed using multiphoton ionization via a favorable UV-absorbing chromophore. Neutral clusters are formed containing the readily ionizable molecule, but the weak interactions between the chromophore and the rest of cluster reduces the extent... 

The neutral clusters, C6H4(OH)2 (H20),, are found to be produced in the gas phase by irradiation of the pulsed IR-laser onto the liquid beam. The clusters continue to be released from the liquid beam surface for a period of 10 ps after the pulsed IR-laser irradiation. The dynamics of the cluster release is further examined by observing the neutral species at a certain time after the IR-laser irradiation at a certain distance from the liquid beam. In reality, the neutral species are ionized by the pulsed UV-laser and are mass analyzed by the mass spectrometer. The spatial distribution of the neutral clusters are observed by changing the position of the ionization laser with respect to the liquid beam and the delay time of the UV-laser irradiation from the IR-laser irradiation. 

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