Laser-Enhanced Ionization Spectroscopy Around the Ionization Limit

Laser-induced photoionization and Laser-Enhanced collision Ionization (LEI) of Na, Tl, and Li in flames are detected by measuring the production of charges following a laser excitation. The ionization signal is investigated for excitations of the atoms from lower lying states both to Rydberg states close to the ionization limit, as well as to continuum states, i.e. the process of collision ionization is compared with that of photoionization. The qualitative behaviour of the ionization signal when scanning across the ionization limit is studied. It is shown that the ionization signal has a smooth behaviour when passing from bound states into continuum states. The laser-induced photoionization signal strength of atoms in flames is both calculated and measured and a good agreement is obtained. A calculation of wavelength dependent photoionization signal strengths for a number of elements is also presented. Photoionization is used to determine flame- and geometry-dependent parameters. An implication of photoionization in connection with LEI spectrometry for trace element analysis is that there will be a significant increase in background noise if the sample contains high concentrations of easily photoionizing elements and short wavelength light is used.