Pulsed field ionization-photoion spectroscopy using two-bunch synchrotron radiation: Time-of-flight selection scheme

We have demonstrated that the time-of-flight (TOF) selection method for pulsed field ionization (PFI) photoelectron detection [Jarvis et al., Rev. Sci. Instrum. 70, 2615 (1999)] can also be applied for the detection of PFI-photoions (PFI-PIs) using the two-bunch synchrotron radiation at the Advanced Light Source. By employing the supersonic beam technique to lower the translational temperature of the sample gas, we show that background prompt ions formed in direct and spontaneous autoionization processes arrive at the ion detector in a pattern similar to that of the vacuum ultraviolet light bunches. The PFI-PIs formed at dark gaps can be designed to arrive at the detector in between adjacent prompt ion peaks, enabling the gating of the PFI-PI signal with only minor contamination from background prompt ions. This experiment has revealed important considerations for the design of a general TOF selection scheme for PFI-PI detection using synchrotron radiation.