Theoretical considerations of laser induced fluorescence and ionization spectrometry: how close to single atom detection

The potential capability of detecting single atoms and/or of approaching the intrinsic detection limit, i.e. the limit where all external causes of noise in the system are eliminated, is discussed with respect to laser induced fluorescence and ionization spectrometry. These approaches have been chosen because of their widespread use in laboratories involved in analytical laser spectroscopy. Among the lasers, tunable dye lasers pumped by N₂, Nd-YAG, Excimer, Cu vapor lasers and flashlamps are considered, and flames, graphite furnaces, plasmas and low pressure glow discharges are considered as atom reservoirs. From practical considerations, it is shown that none of the conventional analytical approaches used can satisfy the requirement of a true single atom detection technique, the only exception being provided by the ionization method coupled with atomization under vacuum.