11
$\begingroup$

What are the signs (if any) in DOS plots that tell us whether we have a big or small crystal-field splitting energy, or spin-splitting energy? I already asked and got an answer to: What do we mean by spin-splitting energy?

I am asking in the context of this paper which discusses a comparison between spin-splitting energy and crystal field splitting energy, and shows multiple DOS plots.

$\endgroup$
1
  • 1
    $\begingroup$ Just a comment: the ligand field theory is inherently a multireference theory, so for quantitative estimations of these energies it is advised to go beyond the energy band model and use a multireference method instead, e.g. use the ab initio ligand field theory (AILFT) method in the ORCA software $\endgroup$
    – wzkchem5
    Nov 14, 2021 at 13:59

1 Answer 1

3
$\begingroup$

I'm going to reproduce the part of my answer from the linked question that relates to the spin-splitting.

I don't believe the spin-splitting or field splitting can be read from the DOS. The way they are mentioned in the paper seems to suggest they are giving a qualitative explanation for seeing all the compounds in high spin configurations. The spectrochemical series gives an ordering of ligands based on how much field splitting they should cause. Since S is known to be a weak-field ligand, it makes sense that the spin splitting energy would be larger than the field splitting, leading to high spin configurations.

As for the crystal-field splitting, perhaps not from the DOS on its own, but the PDOS could help you identify the gap in energy between states formed from different types of d-orbitals.

$\endgroup$

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy

Not the answer you're looking for? Browse other questions tagged or ask your own question.