Title: 

Relativistic Quantum Calculations to Understand the Contribution of f-type Atomic Orbitals and Chemical Bonding of Actinides with Organic Ligands

Year of Publication:

2023

Authors:

Andy D. Zapata-Escobar, Srimanta Pakhira, Joaquin Barroso-Flores, Gustavo Aucar, Jose L Mendoza-Cortes

Journal:

Physical Chemistry Chemical Physics

Abstract:

The nuclear waste problem is one of the main interests of rare earth and actinide element chemistry. Studies of actinide-containing compounds are at the frontier of the applications of current theoretical methods due to the need to consider relativistic effects and approximations to the Dirac equation in them. Here, we employ four-component relativistic quantum calculations and scalar approximations to understand the contribution of f-type atomic orbitals in the chemical bonding of actinides (Ac) to organic ligands. We studied the relativistic quantum structure of an isostructural family made of Plutonium (Pu), Americium (Am), Californium (Cf), and Berkelium (Bk) atoms with the redox-active model ligand DOPO (2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate). Crystallographic structures were available to validate our calculations for all mentioned elements except for Cf. In short, state-of-the-art relativistic …

URL:

https://pubs.rsc.org/en/content/articlehtml/2023/cp/d2cp05399c