Photoionization and fragmentation of alkali metal clusters in supersonic molecular beams

Abstract

A supersonic molecular beam, pulsed laser and time-of-flight mass spectrometer are arranged together in order to study photo- and auto-ionization, two-photon-ionization and fragmentation processes of alkali clusters as a function of the laser wavelength. In spite of an unfavourable duty cycle, however, the apparatus reaches a considerably higher sensitivity than cw experiments. Alkali clustersM _n (n≲21) have been observed and investigated. The well resolved TOF mass spectra are commonly accompanied by significant and broad signals of metastable ions, a phenomenon which cannot be observed by quadrupole mass spectrometry. ParticlesM _n (n≲4) have been investigated by twophoton ionization using two different laser wavelengths. Several new electronic transitions for Na₃ are found; commonly, however, the excitation and ionization channels are accompanied by strong fragmentation processes. The fragment patterns are very sensitively dependent upon the laser wavelength even when working near the ionization threshold. The results are a strong indication, that the peak intensities of cluster mass spectra cannot easily be related to the intensity distribution of the neutral cluster beam.