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The d Orbital Multi Pattern Occupancy in a Partially Filled d Shell: The KFeF 3 Perovskite as a Test Case.

Fabien PascaleSami MustaphaPhilippe D'ArcoRoberto Dovesi
Published in: Materials (Basel, Switzerland) (2023)
The occupancy of the d shell in KFeF3 is t2g4eg2, with five α and one β electrons. The Jahn-Teller lift of degeneracy in the t2g sub-shell produces a tetragonal relaxation of the unit cell (4.09 vs. 4.22 Å, B3LYP result) not observed experimentally. In order to understand the origin of this apparent contradiction, we explored, with a 2 × 2 × 2 supercell (40 atoms per cell), all possible local structures in which contiguous Fe atoms have a different occupancy of the t2g orbitals with the minority spin electron. A total of 6561 configurations (with occupancies from (8,0,0) to (3,2,2) of the 3 t2g orbitals of the 8 Fe atoms) have been explored, with energies in many cases lower (by up to 1550 μEh per 2 Fe atoms) than the one of the fully ordered case, both for the ferromagnetic and the anti-ferromagnetic solutions. The results confirm that the orientation of the β d electron of Fe influences the electrostatics (more efficient relative orientation of the Fe quadrupoles of the d shell) of the system, but not the magnetic interactions. Three hybrid functionals, B3LYP, PBE0, and HSE06, provide very similar results.
Keyphrases
  • density functional theory
  • room temperature
  • metal organic framework
  • single cell
  • cell therapy
  • aqueous solution
  • ionic liquid
  • tandem mass spectrometry