Rigorous Extraction of the Anisotropic Multispin Hamiltonian in Bimetallic Complexes from the Exact Electronic Hamiltonian

Rémi Maurice (1) , Nathalie Guihéry (1) , Roland Bastardis (2) , Cohen de Graaf

1 SEM - Systèmes étendus et magnétisme (LCPQ)
2 LAMPS - LAboratoire de Modélisation Pluridisciplinaire et Simulations

The magnetic anisotropy of the [Ni2(en)4Cl2]2+ (en = ethylenediamine) complex has been studied using wave function based computational schemes. The spin−orbit state interaction methodology provides accurate ab initio energies and wave functions that are used to interpret the anisotropy in bimetallic complexes. The extraction of the anisotropic spin Hamiltonian is performed using the effective Hamiltonian theory. This procedure which has successfully been applied to mononuclear complexes enables one to solve the weak exchange limit. It is shown that the standard coupled spin Hamiltonian only describes a part of the anisotropy of the molecule. Important higher order terms such as the biquadratic anisotropic exchange should be included in the model for an appropriate description of the anisotropy.

Rémi Maurice, Nathalie Guihéry, Roland Bastardis, Cohen de Graaf. Rigorous Extraction of the Anisotropic Multispin Hamiltonian in Bimetallic Complexes from the Exact Electronic Hamiltonian. Journal of Chemical Theory and Computation, 2010, 6 (1), pp.55-65. ⟨10.1021/ct900473u⟩. ⟨hal-00863055⟩