Simulating Transient X-ray Photoelectron Spectra of Fe(CO)5 and Its Photodissociation Products With Multireference Algebraic Diagrammatic Construction Theory

• Published in: arXiv.org 2024-04
• Main Authors: Gaba, Nicholas P, Carlos E V de Moura, Majumder, Rajat, Alexander Yu Sokolov
• Format: Article
• Language: English
• Subjects: Algebra; Carbonyls; Electron spin; Electronic structure; Iron; Metal compounds; Photochemical reactions; Photodissociation; Photoelectrons; Screening; Simulation; Spin-orbit interactions; Transition metal compounds; X ray photoelectron spectroscopy; X ray spectra
• ISSN: 2331-8422
• DOI: 10.48550/arxiv.2402.15599

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 3{\sigma} 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. 149, 044307 (2018)]. 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.