Magnetic properties of Cr₈ and V₈ molecular rings from ab initio calculations

Molecular nanomagnets are systems with a vast phenomenology and are very promising for a variety of technological applications, most notably spintronics and quantum information. Their low-energy spectrum and magnetic properties can be modeled using effective spin Hamiltonians, once the exchange coupling parameters between the localized magnetic moments are determined. In this work we employ density functional theory (DFT) to compute the exchange parameters between the atomic spins for two representative ring-shaped molecules containing eight transition-metal magnetic ions: Cr$_8$ and V$_8$. Considering a set of properly chosen spin configurations and mapping their DFT energies on the corresponding expressions from a Heisenberg Hamiltonian, we compute the exchange couplings between magnetic ions which are first, second and further neighbors on the rings. In spite of their chemical and structural similarities the two systems exhibit very different ground states: antiferromagnetic for Cr$_8$, ferromagnetic for V$_8$, which also features non-negligible couplings between second nearest neighbors. A rationalization of these results is proposed that is based on a multi-band Hubbard model with less-than-half filled shells on magnetic ions.