Attosecond delays between dissociative and non-dissociative ionization of polyatomic molecules

The interplay between electronic and nuclear motions in molecules is a central concept in molecular science. To what extent it influences attosecond photoionization delays is an important, still unresolved question. Here, we apply attosecond electron-ion coincidence spectroscopy and advanced calculations that include both electronic and nuclear motions to study the photoionization dynamics of CH₄ and CD₄ molecules. These molecules are known to feature some of the fastest nuclear dynamics following photoionization. Remarkably, we find no measurable delay between the photoionization of CH₄ and CD₄, neither experimentally nor theoretically. However, we measure and calculate delays of up to 20 as between the dissociative and non-dissociative photoionization of the highest-occupied molecular orbitals of both molecules. Experiment and theory are in quantitative agreement. These results show that, in the absence of resonances, even the fastest nuclear motion does not substantially influence photoionization delays, but identify a previously unknown signature of nuclear motion in dissociative-ionization channels. These findings have important consequences for the design and interpretation of attosecond chronoscopy in molecules, clusters, and liquids.