A high beam energy photoelectron-photofragment coincidence spectrometer for complex anions.

A new high beam energy photoelectron-photofragment coincidence (PPC) spectrometer is described that allows acceleration of heavy anions (>100 amu) to energies in the tens of keV using a linear accelerator (LINAC). High beam energies result in more efficient detection of the neutral photofragments produced via dissociative photodetachment (DPD) of the parent anion and increase the mass range that can be studied with PPC spectroscopy. The novel experimental setup couples an electrospray ionization (ESI) source and a hexapole accumulation trap with a 10-stage LINAC to give a kinematically complete measurement of the dissociation dynamics for heavier anions. ESI dramatically increases the range of anions that can be studied by PPC spectroscopy to include multiply charged anions and larger, more complex molecular ions important in biological, atmospheric, and combustion processes. A radiofrequency buffer-gas-cooled hexapole trap is used to accumulate sufficient ion density for single-shot coincidence measurements and thermalize the anions to room temperature. The photoelectron and up to three neutral fragments resulting from DPD are recorded in coincidence using time and position sensitive detectors. This novel experimental setup is characterized by studying the photodetachment of I-, and the DPD of I 2 - and the oxalate anion C2O4H- at beam energies of 11 keV, 16 keV, and 21 keV.