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

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.