Issue 22, 2024

Simulating transient X-ray photoelectron spectra of Fe(CO)5 and its photodissociation products with multireference algebraic diagrammatic construction theory

Abstract

Accurate simulations of transient X-ray photoelectron spectra (XPS) provide unique opportunities to bridge the gap between theory and experiment in understanding the photoactivated dynamics in molecules and materials. However, simulating X-ray photoelectron spectra along a photochemical reaction pathway is challenging as it requires accurate description of electronic structure incorporating core-hole screening, orbital relaxation, electron correlation, and spin–orbit coupling in excited states or at nonequilibrium ground-state geometries. In this work, we employ the recently developed multireference algebraic diagrammatic construction theory (MR-ADC) to investigate the core-ionized states and X-ray photoelectron spectra of Fe(CO)5 and its photodissociation products (Fe(CO)4, Fe(CO)3) following excitation with 266 nm light. The simulated transient Fe 3p and CO 3σ XPS spectra incorporating spin–orbit coupling and high-order electron correlation effects are shown to be in a good agreement with the experimental measurements by Leitner et al. [J. Chem. Phys., 2018, 149, 044307]. Our calculations suggest that core-hole screening, spin–orbit coupling, and ligand-field splitting effects are similarly important in reproducing the experimentally observed chemical shifts in transient Fe 3p XPS spectra of iron carbonyl complexes. Our results also demonstrate that the MR-ADC methods can be very useful in interpreting the transient XPS spectra of transition metal compounds.

Graphical abstract: Simulating transient X-ray photoelectron spectra of Fe(CO)5 and its photodissociation products with multireference algebraic diagrammatic construction theory

Supplementary files

Article information

Article type
Paper
Submitted
23 Feb 2024
Accepted
21 May 2024
First published
21 May 2024
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2024,26, 15927-15938

Simulating transient X-ray photoelectron spectra of Fe(CO)5 and its photodissociation products with multireference algebraic diagrammatic construction theory

N. P. Gaba, C. E. V. de Moura, R. Majumder and A. Yu. Sokolov, Phys. Chem. Chem. Phys., 2024, 26, 15927 DOI: 10.1039/D4CP00801D

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