Issue 7, 2024

Quantifying the influence of 3d–4s mixing on linearly coordinated metal-ions by L2,3-edge XAS and XMCD

Abstract

The mixing valence d and s orbitals are predicted to strongly influence the electronic structure of linearly coordinated molecules, including transition metals, lanthanides and actinides. In specific cases, novel magnetic properties, such as single-ion magnetic coercivity or long spin decoherence times, ensue. Inspired by how the local coordination symmetry can engender such novel phenomena, in this study, we focus our attention on dopants (Mn, Fe, Co, Ni, Cu) in lithium nitride to accept innovation from molecular magnetism in a high symmetry P6/mmm solid-state crystal. The linear coordination environment results in strong 3d–4s mixing, proving to be an ideal series to investigate the role of d–s mixing and bonding on electronic structure and magnetism. It is shown that L2,3-edge XAS can be applied to experimentally identify the presence of 3d–4s mixing and the influence this has on the ligand-field splitting. XMCD specifies how spin–orbit coupling is affected. The combined spectroscopies are analysed to determine the effect of 4s mixing with support from ab initio calculations. The results provide new insight of relevance to future applications, including quantum information processing and the sustainable replacement of rare earths in magnets.

Graphical abstract: Quantifying the influence of 3d–4s mixing on linearly coordinated metal-ions by L2,3-edge XAS and XMCD

Supplementary files

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Article information

Article type
Edge Article
Submitted
24 Nov 2023
Accepted
22 Dec 2023
First published
26 Dec 2023
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., 2024,15, 2433-2442

Quantifying the influence of 3d–4s mixing on linearly coordinated metal-ions by L2,3-edge XAS and XMCD

M. S. Huzan, T. G. Burrow, M. Fix, F. A. Breitner, S. K. Chong, P. Bencok, M. Aramini, A. Jesche and M. L. Baker, Chem. Sci., 2024, 15, 2433 DOI: 10.1039/D3SC06308A

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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