Application of orthorhombic standardization in magnetic susceptibility studies of localized spin models with S=1, 3/2, 2, 5/2

Abstract

The standardization idea is nowadays tacitly accepted in EMR area, however, its usefulness in magnetism studies has not been fully recognized as yet. This idea arises due to intrinsic features of orthorhombic Hamiltonians of any physical nature, including the crystal (ligand) field (CF/LF) Hamiltonians or the zero-field splitting (ZFS) ones. Standardization limits the ratio of the orthorhombic parameter to the axial one to a fixed range between 0 and a specific value that depends on the notation used. For the ZFS parameters expressed in the conventional spin Hamiltonian (SH) notation the ratio λ=E/D can always be limited to the range (0, ±1/3) by appropriate choice of coordinate system. Implications of standardization of orthorhombic spin Hamiltonians for interpretation of experimental magnetic susceptibility data are considered. Using a numerical example, we show the existence of alternative solutions for ZFS parameters potentially obtainable from fitting experimental magnetic data and discuss their importance. For the first time algebraic applications of the standardization to the expressions for magnetic susceptibility tensor derived earlier for localized spin models with S=1, 3/2, 2, 5/2 and with rhombic anisotropy are explored. The numerical and algebraic results allow us to formulate an 'invariance principle'. These considerations facilitate interpretation of experimental magnetic data and provide an additional check of correctness of analytical magnetic susceptibility expressions.