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The introduction of the pulsed field ionization zero kinetic energy photoelectron spectroscopy technique (referred to as PFI-ZEKE spectroscopy) has resulted in a revolution in photoelectron spectroscopy, because of the tremendous improvement in resolution. This method of threshold photoelectron spectroscopy is based on field ionization of metastable high principal quantum number Rydberg states using a pulsed electric field, delayed from the laser excitation. The detailed mechanism for stabilization of the high principal quantum number Rydberg states has been the subject of a great deal of recent discussion in the literature, and is still somewhat controversial. It is well known that Rydberg state lifetimes scale as n-3, for fluorescence, autoionization, or predissociation, under ideal conditions. This means that for a Rydberg series that can decay by autoionization, if the lifetime of a 5p Rydberg state is 10-12 s, the lifetime of a 150p state will be 10-7 s, which is an order of magnitude shorter than typical delay times used in PFI-ZEKE. The 150p state will be field ionized by an electric field of 0.7 to 1.5 V/cm, which is typical of the pulsed fields used for Stark ionization. This question about Rydberg state lifetimes becomes quite important if one wishes to carry out PFI-ZEKE spectroscopy of ion states well above the lowest ionization threshold, as many decay channels will be available to the Rydberg states converging to the high energy states, resulting in shorter lifetimes for these high energy Rydberg states. Our work in this area has focused largely on PFI-ZEKE spectroscopy at excited state thresholds in molecular ions, where problems of autoionization will be most severe. To reach these high energy thresholds, we have usually used single photon excitation with coherent vacuum ultraviolet light. This excitation method has many advantages.
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