Spectroscopy of the breaking bond: the diradical intermediate of the ring opening in oxazole

Abstract

Bond breaking is a challenging problem in both experimental and theoretical chemistry, due to the transient nature and multi-configurational electronic structure of dissociating molecules. We use anion photodetachment to probe the diradical interactions in the ring-opening reaction of oxazole and obtain a self-consistent picture of the breaking bond. Starting from the closed-shell cyclic molecule, the reaction is launched on the anion potential, as an attached electron cleaves a carbon–oxygen bond. In the photodetachment, two neutral potential regions are sampled. One corresponds to a completely dissociated bond, while the other – to the bond fragments separated by approximately 3 Å. At this chemically relevant distance, signatures of lingering through-space interactions between the radical centers are observed.