Photoionization metal vapors

Figure 1. Schematic illustration of the laser-vaporization supersonic cluster source. Just before the peak of an intense He pulse from the nozzle (at left), a weakly focused laser pulse strikes from the rotating metal rod. The hot metal vapor sputtered from the surface is swept down the condensation channel in dense He, where cluster formation occurs through nucleation. The gas pulse expands into vacuum, with a skinned portion to serve as a collimated cluster bean. The deflection magnet is used to measure magnetic properties, while the final chaiber at right is for measurement of the cluster distribution by laser photoionization time-of-flight mass spectroscopy.

Recently in our laboratory we have initiated a program to study the photoabsorption processes of metal vapors throughout the UV and EUV region. Our research interests are (1) to obtain the absolute cross section measurement of atomic and molecular metal vapors, (2) to study the photoionization processes of molecular metal species, and (3) to study the photodissociation processes of molecular metal ions. Several experimental methods such as the heat-pipe absorption spectroscopy, photoionization mass spectroscopy, and electron-ion coincidence technique, will be used in the study. This report summarizes our first experiment using heat-pipe absorption spectroscopy. 

For the more volatile (alkali) metals it has been possible since the late 1970s to create a beam of cold, naked clusters of 1 < n < 100, where n is the number of atoms per cluster 348, 349). Metal vapor is produced in an oven and then cooled by expansion. The clusters are separated in a time-of-flight mass spectrometer (TOFMS). Later it became possible to handle less volatile (transition) metals through vaporization by a laser beam 347, 350-352). For the mass analysis the neutral clusters are photoionized by a suitable UV laser. 

Two general methods have been proposed for separating uranium isotopes. In the photoionization method to be discussed in Sec. 9.2, in uranium metal vapor is ionized selectively and then separated from unionized by deflection in electric or magnetic fields. In the photochemical method, to be described in Sec. 9.3, UFj in UFj vapor is excited selectively and caused to react chemically to produce a solid lower fluoride, which is then separated from unreacted UF5 vapor. 

Solid samples may be heated and vaporized using laser energy with the additional benefit that compounds may be ionized with the same laser, all at ambient pressure, and characterized in an IMS drift tube. While lasers were used with mobility spectrometers initially for selective photoionization of vapors only,° ° ions were observed from laser contact with solids, including metals and salts. This was not simple vaporization by heating and instead was understood as ablation and ionization. In laser desorption ionization (LDI), the laser pulse initiates a mobility spectrum with a... 

This is a severe drawback in the case of equilibrium studies of metal molecules since, as a rule, such molecules are minor vapor components and maximum sensitivity is required for their thermodynamic evaluation. However, very precise ionization potentials can be measured using photoionization spectroscopy (5,28). Berkowltz (28) reviewed early work concerning alkali metal dimers. Herrmann et al. ( ) have measured the ionization potentials of numerous sodium, potassium and mixed sodium-potassium clusters. For most of these clusters the atomization energies of the neutral molecules are not known. Therefore, the dissociation energies of the corresponding positive ions cannot be calculated. 

Other important GC detectors include the thermionic detector, the electrolytic conductivity or Hall detector, and the photoionization detector. The thermionic detector is similar in construction to the FID. With the thermionic detector, nitrogen- and phosphorus-containing compounds produce increased currents in a flame in which an alkali metal salt is vaporized. The thermionic detector is widely used for organophosphorus pesticides and pharmaceutical compounds. 

While much of the surveyed research exhibits promising vapor-phase sensing performance, many of the technologies remain experimental and bound to a laboratory setting. Most of the commercial gas sensors available today utilize older, more mature technologies such as electrochemical cells, catalytic beads, photoionization detectors (PID), SAW, metal oxide semiconductors (MOS), and QCM. The dearth of viable organic solid-state vapor-phase chemosensors indicates that there is much work still to be done (in terms of material stability, selectivity, etc.) before commercialization becomes commonplace for organic sensors. 

The basic function of the mass spectrometer is to measure the mass-to-charge ratios of analyte ions, and the various designs of mass spectrometers have been described in detail in the literature. The HPLC-MS system has four main components consisting of a sample inlet, an ion source, a mass analyzer, and finally an ion detector. The sample introduction system vaporizes the HPLC column effluent. The ion source produces ions from the neutral analyte molecules in the vapor phase. Several designs of ion sources have been used over the past years including electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), thermospray ionization (TSP), continuous flow fast atom bombardment (FAB), and atmospheric pressure photoionization (APPI). The inductively coupled plasma (ICP) is a hard ionization source and is used specifically for the detection of metals and metals in adducts or in organometallic compounds. Generally, ICP-MS is used for elemental speciation analysis with HPLC, which has been described elsewhere in... 

The AVLIS process consists of a laser system and a separator system. The latter contains a vaporizer and a collector. The working medium is metallic uranium that is melted and vaporized to form an atomic vapor stream. The vapor stream flows through the collector where it is illuminated by precisely tuned laser light. The selected atoms become charged by photoionization and are removed from the vapor stream by an electronic field. 

Using a combination of laser vaporization and molecular beam methods with TOF-MS analysis, plus photoionization, photoelectron spectroscopy, and reactions with small molecules for characterization, Kaya and coworkers were able to produce and characterize several intriguing rare earth organome-tallic clusters with network structures (Nakajima and Kaya, 2000). These studies employed Ceo as a ligand the M-Ceo clusters formed for M = Sc had chain or ring stmctures in which metal atoms and C o were alternately... 

---