Issue 11, 2022

Covalency in actinide(iv) hexachlorides in relation to the chlorine K-edge X-ray absorption structure

Abstract

Chlorine K-edge X-ray absorption near edge structure (XANES) in actinideIV hexachlorides, [AnCl6]2− (An = Th–Pu), is calculated with relativistic multiconfiguration wavefunction theory (WFT). Of particular focus is a 3-peak feature emerging from U toward Pu, and its assignment in terms of donation bonding to the An 5f vs. 6d shells. With or without spin–orbit coupling, the calculated and previously measured XANES spectra are in excellent agreement with respect to relative peak positions, relative peak intensities, and peak assignments. Metal–ligand bonding analyses from WFT and Kohn–Sham theory (KST) predict comparable An 5f and 6d covalency from U to Np and Pu. Although some frontier molecular orbitals in the KST calculations display increasing An 5f–Cl 3p mixing from Th to Pu, because of energetic stabilization of 5f relative to the Cl 3p combinations of the matching symmetry, increasing hybridization is neither seen in the WFT natural orbitals, nor is it reflected in the calculated bond orders. The appearance of the pre-edge peaks from U to Pu and their relative intensities are rationalized simply by the energetic separation of transitions to 6d t2gversus transitions to weakly-bonded and strongly stabilized a2u, t2u and t1u orbitals with 5f character. The study highlights potential pitfalls when interpreting XANES spectra based on ground state Kohn–Sham molecular orbitals.

Graphical abstract: Covalency in actinide(iv) hexachlorides in relation to the chlorine K-edge X-ray absorption structure

Supplementary files

Article information

Article type
Edge Article
Submitted
18 Nov. 2021
Accepted
03 Febr. 2022
First published
09 Febr. 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 3194-3207

Covalency in actinide(IV) hexachlorides in relation to the chlorine K-edge X-ray absorption structure

D. Sergentu and J. Autschbach, Chem. Sci., 2022, 13, 3194 DOI: 10.1039/D1SC06454A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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