High resolution pulsed field ionization photoelectron spectroscopy using multibunch synchrotron radiation: Time-of-flight selection scheme

Abstract

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 multibunch undulator synchrotron radiation at the Advanced Light Source. By employing a simple electron 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(11s′) autoionizing Rydberg peak, which is adjacent to the Ar+(2P3/2) PFI-PE band. The rotational-resolved PFI-PE band for H2+ (X 2Σg+,v+=0) measured using this electron TOF selection scheme is nearly free from residues of nearby autoionizing 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 full width at half maximum (FWHM) and 1.9 cm−1 FWHM in the PFI-PE bands for Xe+(2P3/2) and Ar+(2P3/2) at 12.123 and 15.760 eV, respectively. These resolutions are more than a factor 2 better than those achieved in previous synchrotron based PFI-PE studies.