Implications of Invalid Conversions between Crystal-Field Parameters and Zero-Field Splitting Ones Used in Superposition Model

C. Rudowicza and M. Karbowiakb aInstitute of Physics, West Pomeranian University of Technology, al. Piastów 17, 70-310 Szczecin, Poland bFaculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, Poland

Received: February 17, 2014

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The methodology used in recent study of the zero-field splitting parameters of Cr3+ ions at various orthorhombic symmetry sites in LiKSO4 by Pandey and Kripal is critically commented on. We argue that the crystal field parameters, Bkq, in the Wybourne notation, which were calculated using the superposition model for Cr3+ ions in LiKSO4, may only be converted into the crystal field parameters in the Stevens notation. Regrettably, the authors have also converted the latter parameters supposedly into the zero-field splitting parameters D and E in the conventional notation. Such direct conversions are fundamentally incorrect and constitute factual invalid usage of the conversion relations between the crystal field (ligand field) parameters and the zero-field splitting ones. The cases of an implied usage of the invalid conversion relations between the crystal field parameters and the zero-field splitting parameters occurring in recent literature are also outlined. Pandey and Kripal have found the zero-field splitting parameters theoretically evaluated in this way to be in good agreement with the experimental values. However, the faulty methodology renders the conclusion that Cr3+ ions enter into the LiKSO4 lattice at the substitutional K+ sites unjustified. Several other conceptual problems arising from misinterpretations of the crucial notions identified therein are also discussed and clarified.

DOI: 10.12693/APhysPolA.125.1215 PACS numbers: 76.30.-v, 76.30.Fc, 71.70.Ch, 75.10.Dg