Ultrafast dynamics of low-energy electron attachment via a non-valence correlation-bound state

The primary electron-attachment process in electron-driven chemistry represents one of the most fundamental chemical transformations with wide-ranging importance in science and technology. However, the mechanistic detail of the seemingly simple reaction of an electron and a neutral molecule to form an anion remains poorly understood, particularly at very low electron energies. Here, time-resolved photoelectron imaging was used to probe the electron-attachment process to a non-polar molecule using time-resolved methods. An initially populated diffuse non-valence state of the anion that is bound by correlation forces evolves coherently in ∼30 fs into a valence state of the anion. The extreme efficiency with which the correlation-bound state serves as a doorway state for low-energy electron attachment explains a number of electron-driven processes, such as anion formation in the interstellar medium and electron attachment to fullerenes. The capture of an electron by a molecule represents one of the most fundamental chemical transformations, but its mechanism at very low energies remains unclear. Now, it is shown that low-energy electron attachment to hexafluorobenzene is mediated by a non-valence correlation-bound state of the anion.