Femtosecond Multidimensional Imaging of a Molecular Dissociation

The coupled electronic and vibrational motions governing chemical processes are best viewed from the molecule's point of view-the molecular frame. Measurements made in the laboratory frame often conceal information because of the random orientations the molecule can take. We used a combination of time-resolved photoelectron spectroscopy, multidimensional coincidence imaging spectroscopy, and ab initio computation to trace a complete reactant-to-product pathway-the photodissociation of the nitric oxide dimer-from the molecule's point of view, on the femtosecond time scale. This method revealed an elusive photochemical process involving intermediate electronic configurations.