Séminaire de l’équipe PCMT: Reza Mosaferi Institut des Nanosciences de Paris (INSP) - UMR7588 Sorbonne Université - CNRS

Orateur : Reza Mosaferi (Institut des Nanosciences de Paris (INSP) - UMR7588 Sorbonne Université - CNRS)

Titre : Ab-Initio Study of the Cu 2p core-level XPS spectra of copper complexes

Résumé :

We introduce an ab initio framework that explains the origin of main and satellite features in Cu 2p X-ray photoelectron spectra without invoking the conventional charge-transfer picture. The method combines an in-house configuration-interaction treatment of electronic relaxation and correlation with a determinant-overlap formalism to evaluate intensities between initial and core-ionized states. We show that the satellite band arises from shake-up excitations in which a valence electron is promoted into the singly occupied antibonding orbital (SOMO). Core-hole formation drives a pronounced reorganization of this SOMO—from a Cu-centered antibonding orbital in the ground state to a ligand-dominated orbital in the final state—controlling the main/satellite intensity ratio. The approach is validated on Copper(II) acetylacetonate, where metal–ligand mixing governs the satellite profile, and extended to the liquid-phase Cu(aqua)²⁺ complex, where solvation induces characteristic shifts and spectral reshaping.