Selectivity, specificity, and sensitivity in the photoionization of sputtered species

To deal with the problem of non- or near-resonant ionization, one needs to achieve the highest selectively for photoionization of the species of interest relative to isobarically overlapping species by choosing a specific photoionization scheme tailoring are that is could not have near-overlap with known atomic or molecular energy levels of isobaric species, and that it should lead to saturation of the resonance transitions at the lowest possible laser power levels so as to minimize two- and three-photon nonresonant photoionization processes. Experience has shown that, even when these two conditions are met as closely as possible, non- or near-resonant ionization can still occur, perhaps because of the existence of hitherto unobserved energy levels, photodissociation of sputtered molecules, or other effects. It is becoming clear that maximizing detection sensitivity for a particular species requires one to pay careful attention to the selection of an optimal photoionization scheme. It is the purpose of the present paper to illustrate this point with several examples and to help point the way to still further improvements in detection sensitivity by non- or near-resonant. ionization through detailed exploration of alternative photoionization schemes