Consistent Evaluation of Magnetic Exchange Couplings in Multicenter Compounds in KS-DFT: The Recomposition Method

Abstract

The use of broken-symmetry calculations in Kohn-Sham density functional theory has offered an affordable route to study magnetic exchange couplings in transition-metal-based compounds. However, computing this property in compounds exhibiting several couplings is still challenging and especially due to the difficulties to overcome the well-known problem of spin contamination. Here, we present a new and general method to compute magnetic exchange couplings in systems featuring several spin sites. To provide a consistent spin decontamination of J values, our strategy exploits the decomposition method of the magnetic exchange coupling proposed by Coulaud et al. and generalizes our previous work on diradical compounds where the overall magnetic exchange coupling is defined as the sum of its three main and properly extracted physical contributions (direct exchange, kinetic exchange, and spin polarization). In this aim, the generalized extraction of all contributions is presented to systems with multiple spin sites bearing one unpaired electron. This is done by proposing a new paradigm to treat the kinetic exchange contribution, which proceeds through monorelaxations of the magnetic orbitals. This method, so-called the recomposition method, is applied to a compound featuring three Cu(II) ions with a linear arrangement and to a recently synthesized complex containing a Cu₄O₄ cubane unit presenting an unusual magnetic behavior.