Ferté Anthony, Palaudoux Jérôme, Penent Francis, Iwayama Hiroshi, Shigemasa Eiji, Hikosaka Yasumasa, Soejima Kouichi, Ito Kenji, Lablanquie Pascal, Taïeb Richard, Carniato Stéphane
Laboratoire de Chimie Physique Matière et Rayonnement (LCPMR), Sorbonne Université and CNRS, F-75005 Paris, France.
UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585, Japan.
J Phys Chem Lett. 2020 Jun 4;11(11):4359-4366. doi: 10.1021/acs.jpclett.0c01167. Epub 2020 May 19.
Double core hole spectroscopy is an ideal framework for investigating photoionization shake-up satellites. Their important intensity in a single site double core hole (ssDCH) spectrum allows the exploration of the subtle mix of relaxation and correlation effects associated with the inherent multielectronic character of the shake-up process. We present a high-accuracy computation method for single photon double core-shell photoelectron spectra that combines a selected configuration interaction procedure with the use of non-orthogonal molecular orbitals to obtain unbiased binding energy and intensity. This strategy leads to the oxygen ssDCH spectrum of the CO molecule that is in excellent agreement with the experimental result. Through a combined wave function and density analysis, we highlight that the most intense shake-up satellites are characterized by an electronic reorganization that opposes the core hole-induced relaxation.
