Penning ionization reactions in merged beams with precisely controlled collision energies have been shown to accurately probe quantum mechanical effects in reactive collisions. A complete microscopic understanding of the reaction is, however, faced with two major challenges---the highly excited character of the reactions entrance channel and the limited precision of even the best state-of-the-art ab initio potential energy surfaces. Here, we suggest photoassociation spectroscopy as a tool to identify the character of orbiting resonances in the entrance channel and probe the ionization width as a function of inter-particle separation. We introduce the basic concept and discuss the general conditions under which this type of spectroscopy will be successful.
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