Inner-valence photoionization of HCN: An example of the complete breakdown of the quasiparticle picture of photoionization
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We performed both single- and coupled-channel scattering calculations of the photoionization of HCN at a photon energy range of 401000 eV. Based upon the present results, we predict that HCN is a system for which the inner-valence photoionization is characterized by a complete breakdown of the quasiparticle picture of photoionization. We find that there is no inner valence main line and that the intensity from photoionization from the inner valence 3 orbital is split into two prominent satellites and two weaker satellites. These four satellites occur at binding energies of approximately 27.0, 29.5, 31.0, and 33.0 eV, and are almost solely of inner valence origin. We identify these satellites as being of inner-valence origin as a consequence of the theoretically predicted high-energy convergence of the photoionization cross-section rations to the ratio of corresponding spectroscopic intensity factors. Additionally, we find that there is one mixed provenance satellite that occurs on the shoulder of the highest binding energy [Formula Presented] line at 22.5 eV, i.e., lower than the expected energy range for satellites. The existence of this satellite is another result of the breakdown of the quasiparticle picture. On a phenomenological basis, all four of the inner-valence-derived satellites appear to be dynamically correlated shake-up states. 1999 The American Physical Society.
