Abstract
An analysis of the relationship between the EPR trigonal-field parameters and the local crystal structure of octahedral Mn 2+ centre in diamagnetic garnets is presented by diagonalizing the complete energy matrices for a d 5 configuration ion in a trigonal ligand-field. Both the second-order and fourth-order EPR parameters D and ( a − F) are taken simultaneously into the structural investigation. It is shown that the local lattice structure around an octahedrally coordinated Mn 2+ centre in diamagnetic garnets have expansion distortions, which may be attributed to the fact that the radius of Mn 2+ ion is larger than that of Al 3+ or Ga 3+ ion, and the Mn 2+ ion will push the oxygen ligands outwards. The local lattice structure parameters R and θ for octahedral Mn 2+ ion centre in the crystals are determined, respectively. Meanwhile, it is also demonstrated that the empirical impurity-ligand distance R ≈ R H + 1 2 ( r i - r h ) is not suitable for Mn 2+ in diamagnetic garnets, which has been approximately taken in previous works.
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