Towards simultaneous imaging of ultrafast nuclear and electronic dynamics in small molecules.

When a chemical bond is broken, the molecular structure undergoes a transformation. An ideal experiment should probe the change in the electronic and nuclear structure simultaneously. Here, we present a method for the simultaneous time-resolved imaging of nuclear and electron dynamics by combining Coulomb explosion imaging with strong-field photoelectron momentum imaging. We study the dissociative photoionization of H and NO using time-resolved photoion-photoelectron coincidence spectroscopy. The measured delay-dependent kinetic energy release clearly reveals the ultrafast nuclear dynamics. The transient changes in the electronic structure of the dissociating [Formula: see text] molecular ion are studied by solving the three-dimensional Schrödinger equation in the fixed-nuclei approximation. A detailed comparison of the numerical results to those from a simple imaging model is conducted. The numerical results reflect the evolution in the electron density in the molecular ion as its bond is first stretched and then breaks apart. While these details remain unresolved in the H experiment, we demonstrate the sensitivity of the photoelectron signal to the site of electron localization following bond cleavage for the case of NO. Our work shows opportunities and challenges on the track towards capturing simple gas-phase chemical dynamics in complete molecular movies.