Experimental and Theoretical Investigations of the Second-Order Zero Field Splitting Parameters of Mn(II) with Cl− as Ligand

Zero field splitting (ZFS) parameters for [MnCl6]4- in three Cd compounds were determined and the validity of the superposition model was demonstrated by the consistent values of the intrinsic ZFS parameter b2 in all three cases as well as by a detailed comparison of the experimental ZFS pattern for one compound with that calculated from the crystal structure data. Additional ZFS data for [MnCl6]4- from the literature are also shown to lead to only slightly variable values of b2. – The change of the intrinsic ZFS parameter b2 from a negative value for F− to a larger positive value for Cl− as ligand is shown by detailed calculations for the various mechanisms to be due to the superponable overlap and covalency contributions as a result of increased charge transfer and ligand spin-orbit coupling constant. The reliability of such calculations is still limited by the lack of experimental data for the transferred spin densities.

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