Advanced Computation Method for Double Core Hole Spectra : Insight Into the Nature of Intense Shake-up Satellites

Anthony Ferté (1) , Jerome Palaudoux (1) , Francis Penent (1) , Hiroshi Iwayama (2) , Eiji Shigemasa (2) , Yasumasa Hikosaka (3) , Kouichi Soejima (4) , Kenji Ito (5) , Pascal Lablanquie (1) , Richard Taïeb (1) , Stéphane Carniato (1)

1 LCPMR - Laboratoire de Chimie Physique - Matière et Rayonnement
2 UVSOR - Ultraviolet Synchrotron Orbital Radiation Facility
3 University of Toyama
4 Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization
5 Niigata University

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 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.

Mots clés: CIPSI calculation; Non-orthogonal molecular orbitals; Multi-electron coincidence spectroscopy; Shake-up satellite; Double core hole process

Domaines: Chimie analytique; Chimie théorique et/ou physique

Anthony Ferté, Jerome Palaudoux, Francis Penent, Hiroshi Iwayama, Eiji Shigemasa, et al.. Advanced Computation Method for Double Core Hole Spectra : Insight Into the Nature of Intense Shake-up Satellites. Journal of Physical Chemistry Letters, 2020, pp.4359−4366. ⟨10.1021/acs.jpclett.0c01167⟩. ⟨hal-02614086⟩