Quantifying the influence of 3d-4s mixing on linearly coordinated metal-ions by L 2,3 -edge XAS and XMCD.
Myron S HuzanTimothy G BurrowManuel FixFranziska A BreitnerSut Kei ChongPeter BencokMatteo AraminiAnton JescheMichael L BakerPublished in: Chemical science (2023)
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 P 6/ 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 L 2,3 -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.
Keyphrases
- solid state
- density functional theory
- room temperature
- molecular dynamics
- quantum dots
- single molecule
- metal organic framework
- transition metal
- healthcare
- risk assessment
- social media
- human health
- health information
- molecular dynamics simulations
- heavy metals
- climate change
- drinking water
- health risk
- reduced graphene oxide
- health risk assessment
- tandem mass spectrometry
- monte carlo
- energy transfer