Photon-energy dependence of single-photon simultaneous core ionization and core excitation in CO 2

We have studied the ${K}^{\ensuremath{-}2}V$ process corresponding to simultaneous $K$-shell ionization and $K$-shell excitation in the $\mathrm{C}{\mathrm{O}}_{2}$ molecule. We define these ${K}^{\ensuremath{-}2}V$ states as super shake-up, at variance with the ``conventional'' ${K}^{\ensuremath{-}1}{v}^{\ensuremath{-}1}V$ shake-up states. While the nature and evolution with photon energy of the conventional shake-up satellites has been the object of many studies, no such data on a large photon-energy range were previously reported on super shake-up. The $\mathrm{C}{\mathrm{O}}_{2}$ molecule is a textbook example because it exhibits two well-isolated ${K}^{\ensuremath{-}2}V$ resonances (with V being $2{\ensuremath{\pi}}_{u}^{*}$ and $5{\ensuremath{\sigma}}_{g}^{*}$) with different symmetries resulting from shake-up processes of different origin populated in comparable proportions. The variation of the excitation cross section of these two resonances with photon energy is reported, using two different experimental approaches, which sheds light on the excitation mechanisms. Furthermore, double-core-hole spectroscopy is shown to be able to integrate and even expand information provided by conventional single-core-hole X-ray Photoelectron Spectroscopy (XPS) and Near-Edge X-ray Absorption Fine Structure (NEXAFS) techniques, revealing, for instance, $g\ensuremath{-}g$ dipole forbidden transitions which are only excited in NEXAFS spectra through vibronic coupling.