Coupled-cluster methods for core-hole dynamics

Coupled cluster (CC) is a powerful numerical method used in quantum chemistry in order to take into account electron correlation with high accuracy and size consistency. In the CC framework, excited, ionized, and electron-attached states can be described by the equation of motion (EOM) CC technique. However, bringing CC methods to describe molecular dynamics induced by x rays is challenging. X rays have the special feature of interacting with core-shell electrons that are close to the nucleus. Core-shell electrons can be ionized or excited to a valence shell, leaving a core-hole that will decay very fast (e.g. 2.4 fs for K-shell of Ne) by emitting photons (fluorescence process) or electrons (Auger process). Both processes are a clear manifestation of a many-body effect, involving electrons in the continuum in the case of Auger processes. We review our progress of developing EOM-CC methods for core-hole dynamics. Results of the calculations will be compared with measurements on core-hole decays in atomic Xe and molecular XeF$_2$.