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We have developed an efficient electron time-of-flight (TOF) selection scheme for high resolution pulsed field ionization (PFI) photoelectron (PFI-PE) measurements using monochromatized multi-bunch undulator synchrotron radiation at the Advanced Light Source. By employing a simple electron time-of-flight (TOF) spectrometer, we show that PFI-PEs produced by the PFI in the dark gap of a synchrotron ring period can be cleanly separated from prompt background photoelectrons. A near complete suppression of prompt electrons was achieved in PFI-PE measurements by gating the PFI-PE TOF peak, as indicated by monitoring background electron counts at the Ar(lls') autoionizing Rydberg peak, which is adjacent to the Ar"(2P3/2) PFI-PE band. The rotational-resolved PFI-PE band for Hi* (XSg\ v+=0) measured using this electron TOF selection scheme is nearly free from residues of nearby autoionizating features, which were observed in the previous measurement by employing an electron spectrometer equipped with a hemispherical energy analyzer. This comparison indicates that the TOF PFI-PE scheme is significantly more effective in suppressing the hot-electron background. In addition to attaining a high PFI-PE transmission, a major advantage of the electron TOF scheme is that it allows the use of a smaller pulsed electric field and thus results in a higher instrumental PFI-PE resolution. We have demonstrated instrumental resolutions of 1.0 cm" 1 (FWHM) and 1.9 cm"1 (FWHM) in the PFI-PE bands for Xe~(2P3/2) and Ar^(2P3/2) at 12.123 eV and 15.760 eV, respectively. These resolutions are more than a factor 2 better than those achieved in previous synchrotron based PFI-PE studies.

Rotational-resolved photoelectron spectroscopy and energy-selected photoelectron-photoion coincidence spectroscopy using synchrotron radiation