Unveiling Hidden Shake-Up Features in the Uranyl M 4 -Edge Spectrum

• Published in: JACS Au 2024-03, Vol.4 (3), p.1134-1141
• Main Authors: Ehrman, Jordan N, Shumilov, Kirill, Jenkins, Andrew J, Kasper, Joseph M, Vitova, Tonya, Batista, Enrique R, Yang, Ping, Li, Xiaosong
• Format: Article
• Language: English
• Subjects: cations; chemical calculations; core electron excitation; covalent bonding; electronic structure; elements; heavy element; M-edge spectroscopy; shake-up peaks; X-ray absorption
• ISSN: 2691-3704; 2691-3704
• DOI: 10.1021/jacsau.3c00838

The M -edge high energy resolution X-ray absorption near-edge structure (HR-XANES) spectra of actinyls offer valuable insights into the electronic structure and bonding properties of heavy-element complexes. To conduct a comprehensive spectral analysis, it is essential to employ computational methods that accurately account for relativistic effects and electron correlation. In this work, we utilize variational relativistic multireference configurational interaction methods to compute and analyze the X-ray M -edge absorption spectrum of uranyl. By employing these advanced computational techniques, we achieve excellent agreement between the calculated spectral features and experimental observations. Moreover, the calculations unveil significant shake-up features, which arise from the intricate interplay between strongly correlated 3d core-electron and ligand excitations. This research provides important theoretical insights into the spectral characteristics of heavy-element complexes. Furthermore, it establishes the foundation for utilizing M -edge spectroscopy as a means to investigate the chemical activities of such complexes. By leveraging this technique, we can gain a deeper understanding of the bonding behavior and reactivity of heavy-element compounds.