Abstract

The negative-ion fragmentation of formic acid (HCOOH) is studied with negative- and positive-ion coincidence spectroscopy. We report four-body ionic fragmentation where up to three positive ions are collected in coincidence with one negative ion. We report yields for 21 three-body channels and five four-body channels. More than 80% of all negative-ion fragmentation involves production of O⁻, and it is dominated by complete dissociation of all molecular bonds. Negative-ion creation is most abundant at high-Rydberg resonances and just above the molecule’s core-ionization potentials. The existence of four-body fragmentation channels evidences a strong charge redistribution in the molecule.