Abstract
It is shown that pulsed-field-ionization (PFI) spectroscopy using usual MPI apparatus without any magnetic shielding gives the spectra of molecular cations comparable to those obtained by ZEKE spectroscopy which requires a thorough magnetic shielding. The electrons detected by PFI spectroscopy were proved to come from very high Rydberg states of a neutral molecule near the convergence limit. The potential of PFI spectroscopy for the study of the vibrational structures of cations is demonstrated for the cations of DABCO, 1,2,4,5-tetrafluorobenzene and m-fluorotoluene.
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