Magnetic Anisotropy in a Cubane-like Ni$_4$ Complex: An Ab Initio Perspective

International audienceMagnetic anisotropy, in the absence of an external magnetic field, relates to the degeneracy lift of energy levels. In the standard case of transition metal complexes, this property is usually modeled by an anisotropic spin Hamiltonian and one speaks of “zero-field splitting” (ZFS) of spin states. While the case of mononuclear complexes has been extensively described by means of ab initio quantum mechanical calculations, the literature on polynuclear complexes studied with these methodologies is rather scarce. In this work, advanced multiconfigurational wave function theory methods are applied to compute the ZFS of the ground S = 4 state of an actual tetranickel(II) complex, displaying a magnet behavior below 0.5 K. First, the isotropic couplings are computed in the absence of the spin–orbit coupling operator, in the full complex and also in clusters with only two active nickel(II) centers, confirming the occurrence of weak ferromagnetic couplings in this system. Second, the single-site magnetic anisotropies are computed on a cluster bearing only one active nickel(II) site, showing that the single-site anisotropy axes are not oriented in an optimal fashion for generating a large uniaxial molecular anisotropy. Furthermore, the possibility for involving only a few local orbital excited states in the calculation is assessed, actually opening the way for a consistent and manageable treatment of the ZFS of the ground S = 4 state. Third, multiconfigurational calculations are performed on the full complex, confirming the weak uniaxial anisotropy occurring for this state and also, interestingly, revealing a significant contribution of the lowest-lying orbitally excited S = 3 states. Overall, by comparison with the experiment, the reported results question the common habit of using only one structure, in particular derived from a crystallography experiment, to compute magnetic anisotropy parameters