Fine Structure and the Huge Zero-Field Splitting in Ni

We perform a thorough study of the ground state magnetic properties of nickel-based 3d8 complexes. This includes an in-depth analysis of the contribution of the crystal field, spin exchange and spin-orbit interactions to the ground state magnetic properties. Of particular interest to the current investigation are the presence and occurrence of non-trivial zero-field splitting. The study focuses on the cases of Ni2+ ideal octahedral, trigonal bipyramidal, square planar and tetrahedral geometries. We provide results for the complete energy spectrum, the fine structure related to the ground state and the second set of excited states, low-field magnetic susceptibility and magnetization. In addition, we examine the zero-field fine structure in square pyramidal, trigonal pyramidal and trigonal planar complexes. The obtained results unequivocally show that a moderate or highly coordinated 3d8 complex can neither exhibit spin-orbit-driven large and giant magnetic anisotropy nor a huge zero-field splitting. Moreover, in the trigonal bipyramidal coordination, a fine structure associated to the ground state cannot result from the spin-orbit coupling alone.