The effect of core hole shape on attosecond valence electron dynamics

Rapid X-ray ionization of a core electron is known to induce attosecond motion of valence electrons, but the effect of core-hole shape on the triggered dynamics remains relatively unknown. In this work, the sub-four femtosecond response of prototypical functionalized/heterocyclic/polycyclic molecules was simulated using real-time timedependent density functional theory (RT-TDDFT), a sudden approximation core-hole and phenomenologically Auger Meitner (AM) decay. These molecules included fluorobenzene, chlorobenzene, bromobenzene, phenol, thiophenol, pyridine, phosphorine, and azulene. It is observed that the valence electron dynamics are essentially independent of the core-hole created, provided it is ionized from an inner-shell and not an inner-valence orbital. This has broad implications for free-electron laser studies of X-ray pumped attosecond processes, since the flexibility in edge allows for a wide range of experimental modalities, core-holes with longer AM lifetimes, and molecular targets.